Co-reporter:Wai-Man Cheung, Wai-Hang Chiu, Matthew de Vere-Tucker, Herman H.-Y. Sung, Ian D. Williams, and Wa-Hung Leung
Inorganic Chemistry May 15, 2017 Volume 56(Issue 10) pp:5680-5680
Publication Date(Web):April 21, 2017
DOI:10.1021/acs.inorgchem.7b00281
Heterobimetallic nitrido porphyrin complexes with the [(L)(por)M–N–M′(LOEt)Cl2] formula {por2– = 5,10,15,20-tetraphenylporphyrin (TPP2–) or 5,10,15,20-tetra(p-tolyl)porphyrin (TTP2–) dianion; LOEt– = [Co(η5-C5H5){P(O)(OEt)2}3]−; M = Fe, Ru, or Os; M′ = Ru or Os; L = H2O or pyridine} have been synthesized, and their electrochemistry has been studied. Treatment of trans-[Fe(TPP)(py)2] (py = pyridine) with Ru(VI) nitride [Ru(LOEt)(N)Cl2] (1) afforded Fe/Ru μ-nitrido complex [(py)(TPP)Fe(μ-N)Ru(LOEt)Cl2] (2). Similarly, Fe/Os analogue [(py)(TPP)Fe(μ-N)Os(LOEt)Cl2] (3) was obtained from trans-[Fe(TPP)(py)2] and [Os(LOEt)(N)Cl2]. However, no reaction was found between trans-[Fe(TPP)(py)2] and [Re(LOEt)(N)Cl(PPh3)]. Treatment of trans-[M(TPP)(CO)(EtOH)] with 1 afforded μ-nitrido complexes [(H2O)(TPP)M(μ-N)Ru(LOEt)Cl2] [M = Ru (4a) or Os (5)]. TTP analogue [(H2O)(TTP)Ru(μ-N)Ru(LOEt)Cl2] (4b) was prepared similarly from trans-[Ru(TTP)(CO)(EtOH)] and 1. Reaction of [(H2O)(por)M(μ-N)M(LOEt)Cl2] with pyridine gave adducts [(py)(por)M(μ-N)Ru(LOEt)Cl2] [por = TTP, and M = Ru (6); por = TPP, and M = Os (7)]. The diamagnetism and short (por)M–N(nitride) distances in 2 [Fe–N, 1.683(3) Å] and 4b [Ru–N, 1.743(3) Å] are indicative of the MIV═N═M′IV bonding description. The cyclic voltammograms of the Fe/Ru (2) and Ru/Ru (4b) complexes in CH2Cl2 displayed oxidation couples at approximately +0.29 and +0.35 V versus Fc+/0 (Fc = ferrocene) that are tentatively ascribed to the oxidation of the {LOEtRu} and {Ru(TTP)} moieties, respectively, whereas the Fe/Os (3) and Os/Ru (5) complexes exhibited Os-centered oxidation at approximately −0.06 and +0.05 V versus Fc+/0, respectively. The crystal structures of 2 and 4b have been determined.
Co-reporter:Yat-Ming So, Wa-Hung Leung
Coordination Chemistry Reviews 2017 Volume 340(Volume 340) pp:
Publication Date(Web):1 June 2017
DOI:10.1016/j.ccr.2016.12.009
•Cerium(IV) complexes supported by O-, N- and C-donor ligands are reviewed.•Chelating O-donor ligands can stabilize the +IV state of cerium.•Cerium(IV) can form multiple bonds with carbon, nitrogen and oxygen atoms.•Cerium(IV) oxo complexes exhibit interesting nucleophilic and redox reactivity.Despite widespread applications of tetravalent cerium compounds in organic synthesis and catalysis, the coordination and organometallic chemistry of cerium(IV) complexes has not been well explored, due, in part, to the high oxidizing power of Ce(IV). Using chelating O-donor supporting ligands, stable tetravalent cerium complexes bearing various ligand functionalities have been isolated, thus making it possible to investigate the reaction chemistry of cerium(IV) complexes systematically. This review summarizes the recent developments of the coordination chemistry of cerium(IV) complexes bearing O-, N-, and C-donor ligands. Special attention will be directed to cerium(IV) complexes supported by a tripodal oxygen ligand.Download high-res image (39KB)Download full-size image
Co-reporter:Shiu-Chun So, Wai-Man Cheung, Herman H.-Y. Sung, Ian D. Williams, Wa-Hung Leung
Journal of Organometallic Chemistry 2017 Volume 853(Volume 853) pp:
Publication Date(Web):15 December 2017
DOI:10.1016/j.jorganchem.2017.10.012
•[Pd(PPh3)4]2 reacts with 4-bromo-2,6-di-tert-butylphenol to afford a phosphaquinone.•[M(PPh3)4] (M = Ni, Pt) react with 4-bromo-2,6-di-tert-butylphenol to give a biquinone.•A Ni(II) 4-hydroxyaryl complex has been synthesized by desilylation of a trimethylsiloxyaryl precursor.Attempts have been made to synthesize group 10 metal complexes bearing σ-bonded 4-hydroxyaryl ligands that are potential precursors to metallaquinones. Treatment of 4-bromo-2,6-di-tert-butylphenol with [Pd(PPh3)4] led to formation of the phosphaquinone Ph3P = C6H3tBu2-3,5-O-4 (1), whereas that with [M(PPh3)4] (M = Ni, Pt) yielded the biquinone [C6H3tBu2-3,5-O-4]2 (2). The solid-state structure of 1 features a short C=O double bond and alternate phenyl C-C single and double bonds that are characteristic of quinoidal compounds. Alkylation of [NiCl2(PPh3)2] with (C6H2Me2-3,5-OSiMe3-4)MgBr afforded cis-[Ni(PPh3)2Br(C6H2Me2-3,5-OSiMe3-4)] (3) that reacted with nBu4NF to yield [Ni(PPh3)(C6H2Me2-3,5-OH-4)]2(μ-OH)2 (4) containing a σ-bonded 4-hydroxyaryl ligand.Treatment of 4-bromo-2,6-di-tert-butylphenol with [Pd(PPh3)4] afforded the phosphaquinone Ph3P = C6H3tBu2-3,5-O-4, whereas that with [M(PPh3)4] (M = Ni, Pt) yielded the biquinone [C6H3tBu2-3,5-O-4]2. A Ni(II) 4-hydroxyaryl complex has been synthesized by alkylation of [NiCl2(PPh3)2] with (C6H2Me2-3,5-OSiMe3-4)MgBr, followed by desilylation.Download high-res image (101KB)Download full-size image
Co-reporter:Yat-Ming So, Yang Li, Ka-Chun Au-Yeung, Guo-Cang Wang, Kang-Long Wong, Herman H. Y. Sung, Polly L. Arnold, Ian D. Williams, Zhenyang Lin, and Wa-Hung Leung
Inorganic Chemistry 2016 Volume 55(Issue 20) pp:10003-10012
Publication Date(Web):May 19, 2016
DOI:10.1021/acs.inorgchem.6b00480
The reactivity of the cerium(IV) oxo complex [(LOEt)2CeIV(═O)(H2O)]·MeC(O)NH2 (1; LOEt– = [CoCp{P(O)(OEt)2}3]−, where Cp = η5-C5H5) toward electrophiles and Brønsted acids has been investigated. The treatment of 1 with acetic anhydride afforded the diacetate complex [CeIV(LOEt)2(O2CMe)2] (2). The reaction of 1 with B(C6F5)3 yielded [CeIV(LOEt)2(Me2CONH2)2][B(C6F5)3(OH)]2 (3), in which the [B(C6F5)3(OH)]− anions are H-bonded to the O-bound acetamide ligands. The treatment of 1 with HCl and HNO3 afforded [CeIV(LOEt)2Cl2] and [CeIV(LOEt)2(NO3)2], respectively. Protonation of 1 with triflic acid (HOTf) gave the diaqua complex [CeIV(LOEt)2(H2O)2](OTf)2 (4), in which the triflate anions are H-bonded to the two aqua ligands. The treatment of 1 with phenol afforded the phenoxide complex [CeIV(LOEt)2(OPh)2] (5). The oxo-bridged bimetallic complex [(LOEt)2(Me2CONH2)CeIV(O)NaLOEt] (6) with the Ce–Ooxo and Na–Ooxo distances of 1.953(4) and 2.341(4) Å, respectively, was obtained from the reaction of 1 with [NaLOEt]. Density functional theory calculations showed that the model complex [(LOMe)2CeIV(Me2CONH2)(O)NaLOMe] (6A; LOMe– = [CoCp{P(O)(OMe)2}3]−) contains a polarized Ce═O multiple bond. The energy for dissociation of the {NaLOMe} fragment from 6A in acetonitrile was calculated to be +33.7 kcal/mol, which is higher than that for dissociation of the H-bonded acetamide from [(LOMe)2CeIV(═O)(H2O)]·MeC(O)NH2 (1A) (calculated to be +17.4 kcal/mol). In hexanes containing trace water, complex 1 decomposed readily to a mixture of a tetranuclear cerium(IV) oxo cluster, [CeIV4(LOEt)4(μ4-O)(μ2-O)4(μ2-OH)2] (7), and a cerium(III) complex, [CeIII(LOEt)2(H2O)2][LOEt] [8(LOEt)], whereas the cerium/sodium oxo complex 6 is stable under the same conditions. The crystal structures of 3, 4·H2O, 6, and 8(LOEt) have been determined.
Co-reporter:Kang-Long Wong, Yat-Ming So, Guo-Cang Wang, Herman H.-Y. Sung, Ian D. Williams and Wa-Hung Leung
Dalton Transactions 2016 vol. 45(Issue 21) pp:8770-8776
Publication Date(Web):26 Apr 2016
DOI:10.1039/C6DT00678G
Heterometallic CeIV/M (M = MoVI, ReVII, VV) oxo clusters supported by the Kläui tripodal oxygen ligand [(η5-C5H5)Co{P(O)(OEt)2}3]− (LOEt−) have been synthesized and structurally characterized, and the catalytic activity of the CeIV/VV oxo cluster in the oxidation of thioanisoles has been studied. Treatment of [Ce(LOEt)Cl3] (1) with [Ag2MoO4] afforded the reported CeIV/MoVI cluster [H4(CeLOEt)6Mo9O38] (2), whereas that with [AgReO4] yielded the CeIV/ReVII cluster [{LOEtCe(ReO4)2(H2O)(μ-ReO4)}2] (3) that contains an 8-membered Ce2Re2O4 ring. Treatment of 1 with [Ag3VO4] afforded the CeIV/VV cluster [H2(CeLOEt)4(VO)4(μ4-O)(μ3-O)12] (4) containing a {Ce4V4O13} oxo-metallic core. The solid-state structure of 4 consists of four {VO4}3− units bridged by four {LOEtCe3+} moieties and a μ4-oxo ligand. Each Ce atom in 4 is 9-coordinated, whereas the geometry around each V atom is pseudo square pyramidal with a terminal oxo at the apical position. Cluster 4 is an active catalyst for the oxidation of substituted thioanisoles with tert-butyl hydroperoxide. For example, the oxidation of thioanisole with tert-butyl hydroperoxide in the presence of 0.01 mol% of 4 gave a ca. 30:1 mixture of the sulfoxide and sulfone products in 96% yield.
Co-reporter:Ka-Chun Au-Yeung, Yat-Ming So, Guo-Cang Wang, Herman H.-Y. Sung, Ian D. Williams and Wa-Hung Leung
Dalton Transactions 2016 vol. 45(Issue 13) pp:5434-5438
Publication Date(Web):02 Mar 2016
DOI:10.1039/C6DT00267F
Reactions of [CeIV(LOEt)2Cl2] (LOEt− = [Co(η5-C5H5){P(O)(OEt)2}3]−) and [CeIV2(μ-O){N(Pri2PO)2}4Cl2] with PhIO afford the λ3-iodane complexes [CeIV(LOEt)2{OI(Cl)Ph}2] and [CeIV2{N(Pri2PO)2}3{OI(Cl)Ph}], respectively, whereas that between [CeIV(LOEt)2Cl2] and PhIO2 or excess PhIO yields the λ5-iodane adduct [CeIV(LOEt)2{OI(O)ClPh}2]. The crystal structures of the CeIV λ3- and λ5-iodane complexes have been determined and their oxo transfer reactivities have been investigated.
Co-reporter:Ka-Wang Chan, Wai-Ming Ng, Wai-Man Cheung, Chun-Sing Lai, Herman H.Y. Sung, Ian D. Williams, Wa-Hung Leung
Journal of Organometallic Chemistry 2016 Volume 812() pp:151-157
Publication Date(Web):15 June 2016
DOI:10.1016/j.jorganchem.2016.02.004
•Ruthenium thiolate nitrosyl complexes have been synthesized and structurally characterized.•The outcome of the reaction of Ru(NO)Cl3 with NaSR is dependent on the nature of the thiolate ligand.•C–S cleavage of the tert-butylthiolate ligand results in the formation of a trinuclear ruthenium sulfido cluster.Treatment of Ru(NO)Cl3 with NaSC6F4H (C6F4HSH = 2,3,5,6-tetrafluorothiophenol) afforded the hydroxo-bridged dimer Na(H2O)2[Ru(NO)(SC6HF4)2]2(μ-SC6HF4)2(μ-OH) (Na(H2O)21), in which the {Na(H2O)2}+ moiety binds to the diruthenium core via the μ-hydroxo ligand and three ortho fluorine atoms of the thiolate ligands. Metathesis of Na(H2O)21 with Bun4NBr and Ph4PCl afforded Na-free (Bun4N)[1] and (Ph4P)[1], respectively. Treatment of Ru(NO)Cl3 with NaSBut afforded the trinuclear oxo-sulfido cluster Na(H2O)2[Ru(NO)(SBut)(μ-SBut)]3(μ3-S)(μ3-O) (Na(H2O)22) that contains a trinuclear {Ru3(SBut)3} core capped by a μ3-oxo and a μ3-sulfido ligand. The {Na(H2O)2}+ moiety binds to the triruthenium core via the μ3-oxo and two terminal thiolate ligands. Metathesis of Na(H2O)22 with Bun4NBr gave (Bun4N)[2]. Treatment of Ru(NO)Cl3 with NaStipp (tipp = 2,4,6-triisopropylphenyl) gave mononuclear Ru(NO)(Stipp)3(tippSH) (3). The crystal structures of Na(H2O)21, (Ph4P)[1], and Na(H2O)22 have been determined.Treatment of Ru(NO)Cl3 with NaSC6HF4 (C6HF4SH = 2,3,5,6-tetrafluorothiophenol) afforded dinuclear Na(H2O)[Ru(NO)(SC6HF4)2]2(μ-SC6HF4)2(μ-OH)2, whereas that with NaSBut resulted in C–S cleavage of the thiolate ligand, and formation of a oxo-sulfido cluster, Na(H2O)2[Ru(NO)(SBut)(μ-SBut)]3(μ3-S)(μ3-O). Reaction of Ru(NO)Cl3 with NaStipp (tipp = 2,4,6-triisopropylphenyl) gave mononuclear Ru(NO)(Stipp)3(tippSH).
Co-reporter:Ho-Yuen Ng, Wai-Man Cheung, Enrique Kwan Huang, Kang-Long Wong, Herman H.-Y. Sung, Ian D. Williams and Wa-Hung Leung
Dalton Transactions 2015 vol. 44(Issue 42) pp:18459-18468
Publication Date(Web):24 Sep 2015
DOI:10.1039/C5DT02513C
Ruthenium thio- and seleno-nitrosyl complexes containing chelating sulfur and oxygen ligands have been synthesised and their de-chalcogenation reactions have been studied. The reaction of mer-[Ru(N)Cl3(AsPh3)2] with elemental sulfur and selenium in tetrahydrofuran at reflux afforded the chalcogenonitrosyl complexes mer-[Ru(NX)Cl3(AsPh3)2] [X = S (1), Se (2)]. Treatment of 1 with KN(R2PS)2 afforded trans-[Ru(NS)Cl{N(R2PS)2}2] [R = Ph (3), Pri (4), But (5)]. Alternatively, the thionitrosyl complex 5 was obtained from [Bun4N][Ru(N)Cl4] and KN(But2PS)2, presumably via sulfur atom transfer from [N(But2PS)2]− to the nitride. Reactions of 1 and 2 with NaLOEt (LOEt− = [Co(η5-C5H5){P(O)(LOEt)2}3]−) gave [Ru(NX)LOEtCl2] (X = S (8), Se (9)). Treatment of [Bun4N][Ru(N)Cl4] with KN(R2PS)2 produced RuIV–RuIV μ-nitrido complexes [Ru2(μ-N){N(R2PS)2}4Cl] [R = Ph (6), Pri (7)]. Reactions of 3 and 9 with PPh3 afforded 6 and [Ru(NPPh3)LOEtCl2], respectively. The desulfurisation of 5 with [Ni(cod)2] (cod = 1,5-cyclooctadiene) gave the mixed valance RuIII–RuIV μ-nitrido complex [Ru2(μ-N){N(But2PS)2}4] (10) that was oxidised by [Cp2Fe](PF6) to give the RuIV–RuIV complex [Ru2(μ-N){N(But2PS)2}4](PF6) ([10]PF6). The crystal structures of 1, 2, 3, 7, 9 and 10 have been determined.
Co-reporter:Yat-Ming So, Wai-Hang Chiu, Wai-Man Cheung, Ho-Yuen Ng, Hung Kay Lee, Herman H.-Y. Sung, Ian D. Williams and Wa-Hung Leung
Dalton Transactions 2015 vol. 44(Issue 12) pp:5479-5487
Publication Date(Web):03 Feb 2015
DOI:10.1039/C5DT00093A
Rhenium nitrido complexes containing the Kläui tripodal ligand [Co(η5-C5H5){P(O)(OEt)2}3]− (LOEt−) have been synthesised and their reactions with [IrI(cod)Cl]2 (cod = 1,5-cyclooctadiene) and [RhII2(OAc)4] (OAc− = acetate) have been studied. The treatment of [Bun4N][ReVI(N)Cl4] with NaLOEt in methanol afforded the ReVI nitride [ReVI(LOEt)(N)Cl(OMe)] (1). Reactions of 1 with [IrI(cod)Cl]2 and [RhII2(OAc)4] gave the μ-nitrido complexes [(LOEt)(OMe)ClReVI(μ-N)IrI(cod)Cl] (2) and [RhII2(OAc)4{(μ-N)ReVI(LOEt)(OMe)Cl}2] (4), respectively. [(LOEt)Cl(PPh3)ReV(μ-N)IrI(cod)Cl] (3) and [(LOEt)Cl(PPh3)ReVI(μ-N)IrI(cod)Cl][PF6] (3·PF6) have been synthesised from the reactions of [IrI(cod)Cl]2 with [ReVLOEt(N)Cl(PPh3)] and [ReVILOEt(N)Cl(PPh3)](PF6), respectively. Similarly, the redox pair [RhII2(OAc)4{(μ-N)ReV(LOEt)(PPh3)Cl}2] (5) and [RhII2(OAc)4{(μ-N)ReVI(LOEt)(PPh3)Cl}2](PF6)2 (5·(PF6)2) have been synthesised from the reactions of [Rh2(OAc)4] with [ReVLOEt(N)Cl(PPh3)] and [ReVILOEt(N)Cl(PPh3)](PF6), respectively. While [(LOEt)Cl2RuVI(μ-N)IrI(cod)] (6) was obtained from [RuVI(LOEt)(N)Cl2] and [IrI(cod)Cl]2, the interaction between [RuVI(LOEt)(N)Cl2] and [RhII2(OAc)4] in CH2Cl2 is reversible. The crystal structures of complexes 2, 3, 3·PF6, 5, 5·(PF6)2 and 6 have been determined. X-ray crystallography indicates that the nitrido bridges in 2, 3, 3·PF6 and 6 can be described as MN—Ir (M = Re, Ru) showing Ir–N multiple bond character, whereas the interaction between ReN and Rh in 5 and 5·(PF6)2 is mostly of the donor–acceptor type. The electrochemistry of the Re nitrido complexes has been investigated by cyclic voltammetry.
Co-reporter:Xiao-Yi Yi;Guo-Cang Wang;Ho-Fai Ip;Wai-Yeung Wong;Lizhuang Chen;Herman H. -Y. Sung;Ian D. Williams
European Journal of Inorganic Chemistry 2014 Volume 2014( Issue 35) pp:6097-6103
Publication Date(Web):
DOI:10.1002/ejic.201402772
Abstract
The treatment of [Ce(LOEt)2(NO3)2] (LOEt– = [Co(η5-C5H5){P(O)(OEt)2}3]–) with KMnO4 in water afforded a diamagnetic purple solid 1, which is tentatively formulated as a CeIV permanganate complex, “[Ce(LOEt)2(MnO4)2]”. The ZrIV analogue, [Zr(LOEt)2(MnO4)2] (2), has been prepared similarly from [Zr(LOEt)2(NO3)2] and KMnO4. The recrystallization of 1 from CH2Cl2/hexanes at –18 °C led to the isolation of dinuclear [(CeLOEt)2(μ-LOEt′)2][MnO4]2 (3), which contains the dianionic tripodal ligand [LOEt′]2– ([(η5-C5H5)Co{P(O)(OEt)2}2{P(O)2(OEt)}]2–). The reactions of 1 with K[ReO4] and [NH4][OsO3N] afforded the heterodimetallic complexes [Ce(LOEt)2(ReO4)2] (4) and [Ce(LOEt)2(NOsO3)2] (5), respectively. The crystal structures of 3 and 5 have been determined. Freshly prepared 1 can oxidize alkylbenzenes such as toluene, ethylbenzene, and cumene at room temperature to give the corresponding ketone and/or alcohol products. Ce–LOEt complexes are efficient promoters of the aerobic oxidation of alkylbenzenes by a radical mechanism. For example, cumene in the presence of [Ce(LOEt)2(H2O)2]Cl (1 mM) in air at 100 °C for 10 h afforded a ca. 6:1 mixture of 2-phenyl-2-propanol and acetophenone with a total turnover number of 6810.
Co-reporter:Wai-Man Cheung, Ho-Yuen Ng, Herman H.-Y. Sung, Ian D. Williams, Wa-Hung Leung
Inorganica Chimica Acta 2014 Volume 422() pp:224-227
Publication Date(Web):1 October 2014
DOI:10.1016/j.ica.2014.05.030
•Dinuclear Os(IV) oxo complex with a bidentate sulfur ligand.•Crystal structure of dinuclear Os(IV) oxo complex.•Reaction of the Os(IV) oxo complex to give a heterometallic Os(IV)/Ag(I) complex.The protonation of trans-[Os(OMe)2{N(Pri2PS)2}2] (1) with HBF4, followed by treatment with NH3(g) afforded the oxo-bridged dimer [Os2(μ-O){N(Pri2PS)2}4F2] (2). Reaction of 2 with Ag(OTf) (OTf− = triflate) gave the heterometallic Os(IV)/Ag(I) complex [Os2(μ-O){N(Pri2PS)2}4F2(AgOTf)2] (3), in which each Ag(OTf) moiety binds to three sulfur atoms of two [N(Pri2PS)2]− ligands. The solid-state structures of complexes 2 and 3 have been established by X-ray crystallography.The protonation of trans-[Os(OMe)2{N(Pri2PS)2}2] (1) with HBF4, followed by treatment with NH3(g) afforded the oxo-bridged dimer [Os2(μ-O){N(Pri2PS)2}4F2] (2). Reaction of 2 with Ag(OTf) (OTf− = triflate) gave the heterometallic Os(IV)/Ag(I) complex [Os2(μ-O){N(Pri2PS)2}4F2(AgOTf)2] (3), in which each Ag(OTf) moiety binds to three sulfur atoms of the [N(Pri2PS)2]− ligands.
Co-reporter:Shiu-Chun So, Wai-Man Cheung, Guo-Cang Wang, Enrique Kwan Huang, Man-Kit Lau, Qian-Feng Zhang, Herman H.-Y. Sung, Ian D. Williams, and Wa-Hung Leung
Organometallics 2014 Volume 33(Issue 17) pp:4497-4502
Publication Date(Web):August 19, 2014
DOI:10.1021/om500707e
Tetraarylruthenium(IV) complexes have been synthesized and their migratory insertion, reductive coupling, and bromination reactions investigated. Treatment of [Ru(acac)3] (acac– = acetylacetonate) with RMgBr, followed by column chromatography in air afforded the tetraaryl complexes [RuR4] (R = 2,5-dimethylphenyl (R1); 4-methoxy-2-methylphenyl (R2)). Oxidation of [RuR24] with AgBF4 gave the Ru(V) complex [RuVR24](BF4), which has a measured μeff of 1.8 μB. [RuR4] and can catalyze the oxidation of methyl p-tolyl sulfide with PhIO. Reaction of [RuR24] with PhICl2 led to C–C reductive coupling and the formation of the Ru(II) η6-biaryl complex [(η6-R2-R2)RuCl2]2 (1). Treatment of [RuR14] with excess NO gave the tetranuclear Ru(II) aryl-N-nitrosohydroxylaminato complex [RuR1(N){κ2-O,O′-ON(R1)NO}(μ-NO2)]4 (2). Bromination of [RuR14] with N-bromosuccinimide resulted in formation of [RuR′4] (R′ = 4-bromo-2,5-dimethylphenyl) (3). The crystal structures of [RuR24], [RuR24](BF4), and 1–3 have been determined.
Co-reporter:Yat-Ming So;Dr. Guo-Cang Wang;Dr. Yang Li;Dr. Herman H.-Y. Sung;Dr. Ian D. Williams;Dr. Zhenyang Lin;Dr. Wa-Hung Leung
Angewandte Chemie International Edition 2014 Volume 53( Issue 6) pp:1626-1629
Publication Date(Web):
DOI:10.1002/anie.201309764
Abstract
Whereas terminal oxo complexes of transition and actinide elements are well documented, analogous lanthanide complexes have not been reported to date. Herein, we report the synthesis and structure of a cerium(IV) oxo complex, [CeO(LOEt)2(H2O)]⋅MeC(O)NH2 (1; LOEt−=[Co(η5-C5H5){P(O)(OEt)2}3]−), featuring a short CeO bond (1.857(3) Å). DFT calculations indicate that the hydrogen bond to cocrystallized acetamide plays a key role in stabilizing the CeO moiety of 1 in the solid state. Complex 1 exhibits oxidizing and nucleophilic reactivity.
Co-reporter:Guo-Cang Wang, Herman H. Y. Sung, Feng-Rong Dai, Wai-Hang Chiu, Wai-Yeung Wong, Ian D. Williams, and Wa-Hung Leung
Inorganic Chemistry 2013 Volume 52(Issue 5) pp:2556-2563
Publication Date(Web):February 13, 2013
DOI:10.1021/ic302567e
Heterometallic cerium(IV) perrhenate, permanganate, and molybdate complexes containing the imidodiphosphinate ligand [N(i-Pr2PO)2]− have been synthesized, and their reactivity was investigated. Treatment of Ce[N(i-Pr2PO)2]3Cl (1) with AgMO4 (M = Re, Mn) afforded Ce[N(i-Pr2PO)2]3(ReO4) (2) or Ce2[N(i-Pr2PO)2]6(MnO4)2 (3). In the solid state, 3 is composed of a [Ce2{N(i-Pr2PO)2}6(MnO4)]+ moiety featuring a weak Ce–OMn interaction [Ce–OMn distance = 2.528(8) Å] and a noncoordinating MnO4– counteranion. While 3 is stable in the solid state and acetonitrile solution, it decomposes readily in other organic solvents, such as CH2Cl2. 3 can oxidize ethylbenzene to acetophenone at room temperature. Treatment of 1 with AgBF4, followed by reaction with [n-Bu4N]2[MoO4], afforded [Ce{N(i-Pr2PO)2}3]2(μ-MoO4) (4). Reaction of trans-Ce[N(i-Pr2PO)2]2(NO3)2 (5), which was prepared from (NH4)2Ce(NO3)6 and K[N(i-Pr2PO)2], with 2 equiv of [n-Bu4N][Cp*MoO3] yielded trans-Ce[N(i-Pr2PO)2]2(Cp*MoO3)2 (6). 4 can catalyze the oxidation of methyl phenyl sulfide with tert-butyl hydroperoxide with high selectivity. The crystal structures of complexes 3–6 have been determined.
Co-reporter:Wai-Man Cheung, Enrique Kwan Huang, Jun Zhu, Xiao-Yi Yi, Herman H. Y. Sung, Ian D. Williams, and Wa-Hung Leung
Inorganic Chemistry 2013 Volume 52(Issue 18) pp:10449-10455
Publication Date(Web):September 6, 2013
DOI:10.1021/ic401289k
η5–η1 ring slippage of [OsCp2] (Cp = η5-C5H5) and [Ru(η5-ind)2] (ind = indenyl) resulting from reaction with the ruthenium(VI) nitride [Ru(LOEt)(N)Cl2] (1; LOEt– = [CoCp{P(O)(OEt)2}3]−) is reported. The treatment of [OsCp2] or [Ru(η5-ind)2] with 1 resulted in η5-η1 ring slippage of the cycloolefin ligands and formation of the trinuclear nitrido complexes [Cp(η1-C5H5)Os(NRuLOEtCl2)2] (2) or [(η5-ind)(η1-ind)Ru(NRuLOEtCl2)2] (3). No reactions were found between [OsCp2] and amines, such as pyridine and 2,2′-bipyridyl, or other metal nitrides, such as [Os(LOEt)(N)Cl2], indicating that the electrophilic property of 1 is essential for ring slippage. The crystal structures of 2 and 3 have been determined. The short Os–N distances in 2 [1.833(5) and 1.817(5) Å] and the (ind)Ru–N distances in 3 [1.827(5) and 1.852(5) Å] are indicative of multiple bond character, consistent with density functional theory (DFT) calculations. Therefore, 2 and 3 may be described by two resonance forms: RuVI–MII–RuVI and RuIV–MVI–RuIV (M = Os, Ru). Also, DFT calculations indicate that for the reaction of 1 with [OsCp2] or [Ru(η5-ind)2], η5–η1 ring slippage is energetically more favorable than the η5–η3 counterpart. The driving force for η5–η1 ring slippage is believed to be the formation of the strong M–N (M = Os, Ru) (multiple) bonds. By contrast, the same reaction with acetonitrile is energetically uphill, and thus no ring slippage occurs.
Co-reporter:Enrique Kwan Huang;Wai-Man Cheung;Ka-Wang Chan;Frank Leung-Yuk Lam;Xijun Hu;Qian-Feng Zhang;Ian D. Williams
European Journal of Inorganic Chemistry 2013 Volume 2013( Issue 16) pp:2893-2899
Publication Date(Web):
DOI:10.1002/ejic.201300043
Abstract
The treatment of [Ru(CO)2Cl2]x with 4,4′,4″-tri-tert-butyl-2,2′:6′,6″-terpyridyl (tbtpy) in tetrahydrofuran at reflux afforded trans-[Ru(tbtpy)Cl2(CO)] (1). The alkylation of complex 1 with excess Me3SiCH2MgCl afforded a mixture of trans-[Ru(tbtpy)(CH2SiMe3)2(CO)] (2) and trans-[Ru(tbtpy)(CH2SiMe3)Cl(CO)] (3), whereas complex 3 could be obtained in good yield by the alkylation of complex 1 with 1 equiv. of Me3SiCH2MgCl. On the other hand, the alkylation of 1 with MeLi and PhCH2MgBr afforded the monoalkyl complexes [Ru(tbtpy)(Me)Cl(CO)] (4) and [Ru(tbtpy)(CH2Ph)Cl0.5Br0.5(CO)] (5), respectively. The crystal structure of complex 5 was determined. Complex 2 and the previously prepared mer-[Ru(dtbpy)(CH2SiMe3)3(NO)] (dtbpy = 4,4′-di-tert-butyl-2,2′-bipyridyl) were immobilized on SBA-15 by treating the Ru complexes with SBA-15 in benzene at room temperature. 1H NMR spectroscopy indicated that the reaction of complex 2 and [Ru(dtbpy)(CH2SiMe3)3(NO)] with SBA-15 in C6D6 resulted in the formation of approximately 1 equiv. of SiMe4, which suggests the grafted species are possibly (≡SiO)Ru(tbtpy)(CH2SiMe3)(CO) and (≡SiO)Ru(dtbpy)(CH2SiMe3)2(NO), respectively. The Ru-grafted SBA-15 materials were characterized by IR, reflectance UV/Vis, and X-ray photoelectron spectroscopy as well as transmission electronic microscopy, and their catalytic performance in the oxidation of benzyl alcohol with tert-butyl hydroperoxide was examined.
Co-reporter:Ho-Yuen Ng, Ngai-Man Lam, Min Yang, Xiao-Yi Yi, Ian D. Williams, Wa-Hung Leung
Inorganica Chimica Acta 2013 Volume 394() pp:171-175
Publication Date(Web):1 January 2013
DOI:10.1016/j.ica.2012.07.025
Ruthenium(VI) complexes with a sterically bulky bidentate Schiff base ligand, 2-[(2,6-diisopropylphenyl)imino]methyl-4,6-dibromophenolate (L−), have been synthesized and their reactivity studied. Treatment of [Bun4N][Ru(N)Cl4] in tetrahydrofuran with 2 equivalents of NaL afforded cis-[Ru(N)Cl(L)2] (1) that reacted with Ag(OTf) (OTf− = triflate) in acetone to give trans-[Ru(N)(H2O)L2][OTf] (2). Reactions of complex 1 with Me3NO and elemental sulfur afforded cis-[Ru(NO)(Cl)L2] (3) and cis-[Ru(NS)(Cl)L2] (4), respectively. Reaction of complex 1 with Me3SiN3 in MeCN afforded [Ru(MeCN)(Cl)L2], which could alternatively be prepared by photolysis of complex 3 in CH2Cl2–MeCN with UV light. The crystal structures of complexes 1 and 2 have been determined.Graphical abstractReactions of cis-[Ru(N)(Cl)L2] (HL = 2-[(2,6-diisopropylphenyl)imino]-methyl-4,6-dibromophenol) with Ag(OTf), Me3NO and S8 gave trans-[Ru(N)(H2O)L2][OTf], cis-[Ru(NO)(Cl)L2] and cis-[Ru(NS)(Cl)L2], respectively.Highlights► Ru(VI) nitrido complexes with a bulky bidentate Schiff base ligand. ► Structurally characterized Ru(VI) nitrido complexes. ► Reactions of Ru(VI) nitrido complexes with Me3NO and S8.
Co-reporter:Enrique Kwan Huang, Wai-Man Cheung, Herman H. Y. Sung, Ian D. Williams, and Wa-Hung Leung
Organometallics 2013 Volume 32(Issue 3) pp:733-736
Publication Date(Web):January 24, 2013
DOI:10.1021/om301114p
The reaction of the RuVI nitride LOEtRuVI(N)Cl2 (1; LOEt– = [Co(η5-C5H5){P(O)(OEt)2}3]−) with RhIII(mes)3 (mes = mesityl) results in insertion of the Ru≡N group into the Rh–C bonds and formation of trinuclear (LOEt)ClRuIV(μ-Cl)(μ-2-CH2-4,6-Me2C6H2N)RhIII(μ-Nmes)(μ-Cl)2RuIV(LOEt) (2), containing a cyclometalated μ-mesitylimido ligand, whereas that with IrIII(dtbpy)R3 gives the μ-nitrido complexes (dtbpy)R3IrIII(μ-N)RuIVCl2(LOEt) (dtbpy = 4,4′-di-tert-butyl-2,2′-bipyridyl; R = 2,5-dimethylphenyl (3), 4-methoxy-2-methylphenyl (4)). The crystal structures of 2 and 4 have been determined.
Co-reporter:Enrique Kwan Huang, Wai-Man Cheung, Sharon Lai-Fung Chan, Herman H. Y. Sung, Ian D. Williams, and Wa-Hung Leung
Organometallics 2013 Volume 32(Issue 16) pp:4483-4489
Publication Date(Web):August 14, 2013
DOI:10.1021/om400183n
The alkylation of [Ru(NPPh3)(PPh3)2Cl3] with Me3SiCH2MgCl afforded the RuIV trialkyl complex [Ru(CH2SiMe3)3(PPh3)Cl] (1), which exhibits a trigonal bipyramidal geometry with the three alkyl groups occupying the equatorial plane. DFT calculations reveal that 1 possesses a (dxz,dyz)4 singlet ground state, consistent with the observed diamagnetism of the complex. The electronic spectrum of 1 displayed two absorptions at 455 and 505 nm, which, on the basis of TDDFT calculations, are attributed to metal-centered d–d transitions with a significant contribution from the alkyl ligands. Chloride abstraction of 1 with Ag(OTf) (OTf– = triflate) provided the triflate complex [Ru(CH2SiMe3)3(PPh3)(OTf)] (2) that proved to be a useful starting material for RuIV trialkyl complexes. Substitution of 2 with NaX afforded [Ru(CH2SiMe3)3(PPh3)(X)] (X = N3– (3) or SCN– (4)). Treatment of 2 with excess sodium 2,3,5,6-tetrafluorophenoxide (NaORf) in tetrahydrofuran resulted in desilylation of two alkyl groups, and formation of the dimethyl complex [Ru(CH2SiMe3)Me2(PPh3)(ORf)] (5). 2 underwent reductive elimination of the C–C bond with 1,10-phenanthroline (phen) in CH2Cl2 to give cis-[Ru(phen)2(PPh3)Cl](OTf) (6). The crystal structures of 1, 2, 4, and 5 have been determined.
Co-reporter:Xiao-Yi Yi, Ho-Yuen Ng, Wai-Man Cheung, Herman H. Y. Sung, Ian D. Williams, and Wa-Hung Leung
Inorganic Chemistry 2012 Volume 51(Issue 20) pp:10529-10535
Publication Date(Web):September 21, 2012
DOI:10.1021/ic300638r
Dinuclear ruthenium nitrido complexes supported by the Kläui’s tripodal ligand [CpCo{P(O)(OEt)2}3]− (LOEt–) have been synthesized starting from the ruthenium(VI) nitrido precursor [LOEtRuVI(N)Cl2] (1). Heating a solution of 1 in CCl4 at reflux, followed by recrystallization from hexane under nitrogen, afforded the mixed-valence ruthenium(V)–ruthenium(IV) μ-nitrido complex [LOEtCl2RuV(μ-N)RuIVCl2LOEt] (2). The cyclic voltammogram of 2 exhibited reversible couples at 0.19 and 1.13 V versus Cp2Fe+/0, which are assigned as the RuV–RuIV/RuIV–RuIV and RuV–RuV/RuV–RuIV couples, respectively. Recrystallization of 2 from Et2O/heptane in air yielded the diamagnetic RuIV–RuIV complex [H13O6][{LOEtRuIVCl2}2(μ-N)] ([H13O6][2]), which underwent cation exchange with n-Bu4NOH to give [n-Bu4N][2]. X-ray diffraction revealed that the complex anions in [H13O6][2] and [n-Bu4N][2] contain linear, symmetric Ru–N–Ru bridges. Treatment of 1 with [(η6-p-cymene)RuIICl2]2 in benzene afforded the tetranuclear ruthenium(IV) complex [LOEtCl2RuIV(μ-N)RuIV(H2O)Cl2]2 (3) containing symmetric RuIV–N–RuIV bridges. The reaction of 1 with [RuII(H)(Cl)(CO)(PCy3)2] (Cy = cyclohexyl) gave the ruthenium(VI)–ruthenium(II) nitrido complex [LOEtCl2RuVI(μ-N)RuII(H)Cl(CO)(PCy3)2] (4). The observed short RuII–N bond distance [1.915(5) Å] and high C–O stretching frequency (1985 cm–1) in 4 are suggestive of π interaction between RuII and the nitride.
Co-reporter:Guo-Cang Wang, Herman H. Y. Sung, Ian D. Williams, and Wa-Hung Leung
Inorganic Chemistry 2012 Volume 51(Issue 6) pp:3640-3647
Publication Date(Web):February 29, 2012
DOI:10.1021/ic202564h
Dinuclear Ti(IV), Zr(IV), and Ce(IV) oxo and peroxo complexes containing the imidodiphosphinate ligand [N(i-Pr2PO)2]− have been synthesized and structurally characterized. Treatment of Ti(O-i-Pr)2Cl2 with KN(i-Pr2PO)2 afforded the Ti(IV) di-μ-oxo complex [Ti{N(i-Pr2PO)2}2]2(μ-O)2 (1) that reacted with 35% H2O2 to give the peroxo complex Ti[N(i-Pr2PO)2]2(η2-O2) (2). Treatment of HN(i-Pr2PO)2 with Zr(O-t-Bu)4 and Ce2(O-i-Pr)8(i-PrOH)2 afforded the di-μ-peroxo-bridged dimers [M{N(i-Pr2PO)2}2]2(μ-O2)2 [M = Zr (3), Ce (4)]. 4 was also obtained from the reaction of Ce[N(i-Pr2PO)2]3 with 35% H2O2. Treatment of (Et4N)2[CeCl6] with 3 equiv of KN(i-Pr2PO)2 afforded Ce[N(i-Pr2PO)2]3Cl (5). Reaction of (Et4N)2[CeCl6] with 2 equiv of KN(i-Pr2PO)2 in acetonitrile, followed by treatment with Ag2O, afforded the μ-oxo-bridged complex [Ce{N(i-Pr2PO)2}Cl]2[μ-N(i-Pr2PO)2]2(μ-O) (6). 6 undergoes ligand redistribution in CH2Cl2 in air to give 5. The solid-state structures of [K2{N(i-Pr2PO)2}2(H2O)8]n and complexes 1–6 have been determined.
Co-reporter:Ho-Fai Ip;Yat-Ming So;Hung Kay Lee;Ian D. Williams
European Journal of Inorganic Chemistry 2012 Volume 2012( Issue 20) pp:3289-3295
Publication Date(Web):
DOI:10.1002/ejic.201200138
Abstract
Iridium and rhodium complexes containing the Kläui oxygen tripodal ligand [Co(η5-C5H5){P(O)(OEt)2}3]– (LOEt–) have been synthesized and their redox chemistry investigated. Treatment of [Ir(COE)2Cl]2 (COE = cyclooctene) with [AgLOEt] afforded [Ir(LOEt)Cl2(COE)] (1), which reacted with AgNO3, 4,4′-di-tert-butyl-2,2′-bipyridyl (dtbpy), and NH4PF6 to give [Ir(LOEt)(dtbpy)(COE)][PF6] (2). Ozonolysis of complex 1 in CH2Cl2 afforded the IrIV complex [Ir(LOEt)Cl3] (3), which exhibited an EPR signal (CH2Cl2, 4 K) with g = 1.65 and 1.06. The IrIV/IrIII reduction potential for complex 3 in acetonitrile was determined to be ca. 0 V vs. ferrocenium/ferrocene. Treatment of [Rh(bpy)Cl3(DMF)] (bpy = 2,2′-bipyridyl; DMF = N,N-dimethylformamide) with [AgLOEt] and Ag(OTf) (OTf– = triflate) afforded [Rh(LOEt)(bpy)Cl][OTf] (4), which reacted with AgOTf in refluxing acetone to yield [Rh(LOEt)(bpy)(acetone)][OTf]2 (5). Reaction of [RhLOEtCl2]2 with 1 equiv. or an excess of tert-butylamine in refluxing tetrahydrofuran afforded [Rh(LOEt)Cl2(NH2tBu)] (6) or [Rh(LOEt)Cl2(NH2tBu)2] (7). Complex 7 contains one chlorido ligand and one noncoordinated chloride ion that is hydrogen-bonded to the two tert-butylamine ligands. The crystal structures of complexes 1, 3, and 7 were determined.
Co-reporter:Ho-Fai Ip, Yat-Ming So, Herman H. Y. Sung, Ian D. Williams, and Wa-Hung Leung
Organometallics 2012 Volume 31(Issue 19) pp:7020-7023
Publication Date(Web):September 18, 2012
DOI:10.1021/om300499x
Reaction of [LOEtRuCl2]2 (LOEt– = [CpCo{P(O)(OEt)2}3]−) (1) with the organic azides RN3 in CH2Cl2 at room temperature, followed by recrystallization from Et2O, afforded [LOEtRuCl2(NH2R)] (R = Ph (2), 4-NO2C6H4 (3), 1-adamantyl (Ad) (4)). Complex 1 can catalyze the reduction of 4-nitrophenyl azide to 4-nitroaniline by cyclohexene. Heating 1 with AdN3 in toluene at reflux led to formation of the cyclometalated Ru(III) complex [LOEtRu(κ2C,N-AdN═CHC6H4)Cl] (5), possibly via double C–H activation of toluene by an imido intermediate. The crystal structures of 3 and 5 have been determined.
Co-reporter:Guo-Cang Wang, Xiao-Yi Yi, Ian D. Williams, and Wa-Hung Leung
Inorganic Chemistry 2011 Volume 50(Issue 18) pp:9141-9146
Publication Date(Web):August 3, 2011
DOI:10.1021/ic201351j
Bismuth(III) compounds containing the Kläui’s oxygen tripodal ligand [CpCo{P(O)(OEt)2}3]− (LOEt–) have been synthesized, and their interactions with dichromate in aqueous media were studied. The treatment of Bi5O(OH)9(NO3)4 with NaLOEt in water afforded [LOEtBi(NO3)2]2 (1), whereas that of BiCl3 with NaLOEt in CH2Cl2 yielded LOEtBiCl2 (2). Chloride abstraction of 2 with AgX afforded [LOEtBiX2]2 [X– = triflate (OTf−) (3), tosylate (OTs−) (4)]. In aqueous solutions at pH > 4, 4 underwent ligand redistribution to give the bis(tripod) complex [(LOEt)2Bi(H2O)][OTs] (5). The treatment of 4 with Na2Cr2O7 in acetone/water afforded the Bi(III)/Cr(VI) oxo cluster [(LOEt)4Bi4(μ3-CrO4)2(μ3-Cr2O7)2] (6) containing a unique Bi4Cr4O12 oxometallic core. Compound 6 oxidized benzyl alcohol to give ca. 6 equiv of benzaldehyde. The reaction between 2 and CrO3 yielded [LOEtBi(OCrO2Cl)]2(μ-Cl)2 (7). The crystal structures of complexes 4–7 have been determined.
Co-reporter:Xiao-Yi Yi ; Ho-Yuen Ng ; Ian D. Williams
Inorganic Chemistry 2011 Volume 50(Issue 4) pp:1161-1163
Publication Date(Web):January 21, 2011
DOI:10.1021/ic101520g
The treatment of [Ru(LOEt)(N)Cl2] (1; LOEt− = [Co(η5-C5H5){P(O)(OEt)2}3]−) with Et3SiH affords [Ru(LOEt)Cl2(NH3)] (2), whereas that with [Ru(LOEt)(H)(CO)(PPh3)] (3) gives the dinuclear imido complex [(LOEt)Cl2Ru(μ-NH)Ru(CO)(PPh3)(LOEt)] (4). The imido group in 4 binds to the two ruthenium atoms unsymmetrically with Ru−N distances of 1.818(6) and 1.952(6) Å. The reaction between 1 and 3 at 25 °C in a toluene solution is first order in both complexes with a second-order rate constant determined to be (7.2 ± 0.4) × 10−5 M−1 s−1.
Co-reporter:Ho-Fai Ip, Xiao-Yi Yi, Wai-Yeung Wong, Ian D. Williams and Wa-Hung Leung
Dalton Transactions 2011 vol. 40(Issue 41) pp:11043-11050
Publication Date(Web):19 Sep 2011
DOI:10.1039/C1DT10306G
Ruthenium nitrosyl complexes containing the Kläui's oxgyen tripodal ligand LOEt− ([CpCo{P(O)(OEt)2}3]− where Cp = η5-C5H5) were synthesized and their photolysis studied. The treatment of [Ru(N⁁N)(NO)Cl3] with [AgLOEt] and Ag(OTf) afforded [LOEtRu(N⁁N)(NO)][OTf]2 where N⁁N = 4,4′-di-tert-butyl-2,2′-bipyridyl (dtbpy) (2·[OTf]2), 2,2′-bipyridyl (bpy) (3·[OTf]2), N,N,N′N′-tetramethylethylenediamine (4·[OTf]2). Anion metathesis of 3·[OTf]2 with HPF6 and HBF4 gave 3·[PF6]2 and 3·[BF4]2, respectively. Similarly, the PF6− salt 4·[PF6]2 was prepared by the reaction of 4·[OTf]2 with HPF6. The irradiation of [LOEtRu(NO)Cl2] (1) with UV light in CH2Cl2-MeCN and tetrahydrofuran (thf)-H2O afforded [LOEtRuCl2(MeCN)] (5) and the chloro-bridged dimer [LOEtRuCl]2(μ-Cl)2 (6), respectively. The photolysis of complex [2][OTf]2 in MeCN gave [LOEtRu(dtbpy)(MeCN)][OTf]2 (7). Refluxing complex 5 with RNH2 in thf gave [LOEtRuCl2(NH2R)] (R = tBu (8), p-tol (9), Ph (10)). The oxidation of complex 6 with PhICl2 gave [LOEtRuCl3] (11), whereas the reduction of complex 6 with Zn and NH4PF6 in MeCN yielded [LOEtRu(MeCN)3][PF6] (12). The reaction of 3·[BF4]2 with benzylamine afforded the μ-dinitrogen complex [{LOEtRu(bpy)}2(μ-N2)][BF4]2 (13) that was oxidized by [Cp2Fe]PF6 to a mixed valence RuII,III species. The formal potentials of the RuLOEt complexes have been determined by cyclic voltammetry. The structures of complexes 5,6,10,11 and 13 have been established by X-ray crystallography.
Co-reporter:Wai-Man Cheung, Xiao-Yi Yi, Guo-Cang Wang, Ian D. Williams, Wa-Hung Leung
Journal of Organometallic Chemistry 2011 696(25) pp: 4007-4010
Publication Date(Web):
DOI:10.1016/j.jorganchem.2011.06.050
Co-reporter:Xiao-Yi Yi ; Tony C. H. Lam ; Ian D. Williams
Inorganic Chemistry 2010 Volume 49(Issue 5) pp:2232-2238
Publication Date(Web):February 4, 2010
DOI:10.1021/ic902018u
The treatment of HfCl4 with NaLOEt (LOEt− = [(η5-C5H5)Co{P(O)(OEt)2}3]−) in nitric acid afforded LOEtHf(NO3)3 (1). Hydrolysis of 1 in acetone/water (4:1, v/v) yielded the hydroxy-bridged dimer [(LOEt)2Hf2(H2O)4(μ-OH)2][NO3]4 (2). The treatment of (NH4)2[Ce(NO3)6] with 2 equiv of NaLOEt in water afforded (LOEt)2Ce(NO3)2 (3), whereas that with 1 equiv of NaLOEt in CH2Cl2 gave LOEtCe(NO3)3 (4). While 4 is stable in organic solvents such as acetone, it was converted completely to 3 in acetone/water. The treatment of 3 with bis(p-nitrophenyl)phosphate (BNPP) afforded (LOEt)2Ce[η1-OPO(OR)2]2 (5; R = p-NO2C6H4), whereas the reaction of 4 with NaPO2(OR)2 yielded dinuclear [LOEtCe(NO3)2{μ-O2P(OR)2}]2 [R = p-NO2C6H4 (6), Ph (7)]. The addition of 3 in acetone to an aqueous solution of NaH2PO4 yielded the cerium(IV) dihydrogen phosphate complex (LOEt)2Ce(PO4H2)2 (8). Complexes 1−5 and 7 have been characterized by X-ray crystallography. The hydrolysis of BNPP with LOEtM(NO3)3 (M = Zr, Hf, Ce) in acetone/water has been studied by 1H NMR spectroscopy. At 25 °C, with [Ce] = 20[BNPP], in an acetone-d6/N-(2-hydroxyethyl)piperazine-N′-2-ethanesulfonic acid (4:1, v/v) buffer solution (50 mM) (4:1, v/v), the hydrolysis of BNPP with 4 was found to exhibit first-order kinetics with a rate constant of (1.1 ± 0.1) × 10−3 s−1.
Co-reporter:Xiao-Yi Yi;Ka-Wang Chan;Enrique Kwang Huang;Yiu-Keung Sau;Ian D. Williams
European Journal of Inorganic Chemistry 2010 Volume 2010( Issue 16) pp:2369-2375
Publication Date(Web):
DOI:10.1002/ejic.201000041
Abstract
Heating [Rh(dtbpy)(κ2-C,C′-CH2CMe2C6H4)(CH2CMe2Ph)] (1; dtbpy = 4,4′-di-tert-butyl-2,2′-bipyridyl) in p-xylene at 110 °C resulted in the formation of the 2-tert-butylphenyl complex [Rh(dtbpy)(κ2-C,C′-CH2CMe2C6H4)(C6H4tBu-2)] (3). Treatment of complex 1 with diethyl phosphite gave the phosphito-bridged dimer [Rh(dtbpy)(κ2-C,C′-CH2CMe2C6H4){P(O)(OEt)2}]2 (4). Refluxing [Ir(dtbpy)(κ2-C,C′-CH2CMe2C6H4)(C6H4tBu-2)] (2) with 2-phenylpyridine (ppyH) and 4-(2-pyridyl)benzaldehyde in toluene followed by column chromatography afforded [Ir(dtbpy)(CH2CMe2Ph)Cl(κ2-N,C-ppy)] (5) and the carbonyl complex [Ir(dtbpy)(CH2CMe2Ph)(CO)(R)] (6) [R = 4-(2-pyridyl)phenyl], respectively. Anion metathesis of [M(dtbpy)(CH2CMe2Ph)(H2O)(OTs)2] with NaBArF4 [ArF = 3,5-(CF3)2C6H3] afforded cationic [M(dtbpy)(CH2CMe2Ph)(H2O)(μ-OTs)]2[BArF4]2 [M = Rh (7), Ir (8)] that are capable of catalyzing H/D exchange of tetrahydrofuran by using D2O as the deuterium source. The crystal structures of complexes 4–7 were determined.
Co-reporter:Wai-Hang Chiu, Qian-Feng Zhang, Ian D. Williams and Wa-Hung Leung
Organometallics 2010 Volume 29(Issue 11) pp:2631-2633
Publication Date(Web):May 11, 2010
DOI:10.1021/om100142d
Treatment of [Et4N]2[WSe4] with dimethyl acetylenedicarboxylate (DMA) afforded the alkyne diselenolene complex [Et4N]2[W(η2-DMA){Se2C2(CO2Me)2}2] (1) along with a minor product, [Et4N]2[W(Se){Se2C2(CO2Me)2}2] (2). The crystal structures of both complexes have been determined by X-ray crystallography. Complex 1 is best described as a metallacyclopropene with two ene-diselenolate ligands.
Co-reporter:Wai-Man Cheung, Wai-Hang Chiu, Xiao-Yi Yi, Qian-Feng Zhang, Ian D. Williams and Wa-Hung Leung
Organometallics 2010 Volume 29(Issue 8) pp:1981-1984
Publication Date(Web):March 29, 2010
DOI:10.1021/om100054n
Treatment of Ru(═CHPh)Cl2(PCy3)2 (Cy = cyclohexyl) with K[N(i-Pr2PS)2] afforded a mixture of Ru(═CHPh)[N(i-Pr2PS)2](PCy3)Cl (1) and Ru(═CHPh)[N(i-Pr2PS)2]2 (2). Reaction of 1 with TlOPh gave Ru(═CHPh)[N(i-Pr2PS)2](PCy3)(OPh) (3), whereas that with NaOMe yielded the Ru(II) hydride compound Ru(H)[N(i-Pr2PS)2][PCy2(η2-C6H9)] (4), in which the dicyclohexyl(cyclohex-3-enyl)phosphine ligand binds to Ru via the phosphorus atom and the C═C bond of the cyclohex-3-enyl ring. The structures of complexes 3 and 4 have been established by X-ray crystallography.
Co-reporter:Yiu-Keung Sau, Xiao-Yi Yi, Ka-Wang Chan, Chun-Sing Lai, Ian D. Williams, Wa-Hung Leung
Journal of Organometallic Chemistry 2010 695(9) pp: 1399-1404
Publication Date(Web):
DOI:10.1016/j.jorganchem.2010.02.002
Co-reporter:Xiao-Yi Yi;Ho-Yuen Ng;Chun-Sing Lai;Ian D. Williams
Science China Chemistry 2010 Volume 53( Issue 10) pp:2139-2143
Publication Date(Web):2010 October
DOI:10.1007/s11426-010-4090-0
Treatment of Ru(CO)(Cl)(H)(PPh3)3 with NaLOEt (LOEt− = [CpCo{P(O)(OEt)2}3]−) afforded the hydride complex (PPh3)(CO)-LOEtRu(H) (1), which has been characterized by X-ray crystallography. Similarly, the tricyclohexylphosphine analogue, (PCy3)(CO)LOEtRu(H) (2), was synthesized from Ru(CO)Cl(H)(PCy3)2 and NaLOEt. Treatment of complex 1 with R’sO2N3 afforded the (arylsulfonyl)amido complexes LOEtRu(CO)(PPh3)(NHSO2R) (R = 2,4,6-i-Pr3C6H2 (3), 4-t-BuC6H4 (4)). The crystal structure of complex 3 has been determined. The Ru-N distance and Ru-N-S angle in 3 are 2.076(3) Å and 126.14(16)°, respectively. Reactions of complex 1 with acids have been studied.
Co-reporter:Wai-Man Cheung;Wai-Hang Chiu;Ian D. Williams
European Journal of Inorganic Chemistry 2009 Volume 2009( Issue 6) pp:792-798
Publication Date(Web):
DOI:10.1002/ejic.200800731
Abstract
Treatment of [Ru(η6-C6Me6)Cl2]2 with AgOTf (OTf– = triflato) followed by K[N(R2PQ)2] gave the 16-electron complexes [Ru(η6-C6Me6){η2-N(R2PQ)2}][OTf] [Q = S, R = Ph (1) or iPr (2); Q = Se, R = Ph (3) or iPr (4)] which were isolated as air-stable blue or dark green crystals. For complex 1, when the crude product was recrystallised from CH2Cl2/hexane in air, orange crystals of [Ru(η6-C6Me6){η3-N(Ph2PS)2}][OTf] (1a) were isolated as a minor product. The reaction of compound 1 with ammonia, hydrazine hydrate and 4,4′-bipyridyl(4,4′-bpy) gave the 18-electron adducts [Ru(η6-C6Me6){η2-N(Ph2PS)2}L][OTf] [L = NH3 (5), N2H4 (6)] and dinuclear[{Ru(η6-C6Me6)[η2-N(Ph2PS)2]}2(μ-4,4′-bpy)][OTf]2 (7), respectively. Treatment of compound 2 with Li[BEt3H] and NaBH4 afforded the ethyl [Ru(η6-C6Me6){N(iPr2PS)2}Et] (8) andhydride [Ru(η6-C6Me6){η2-N(iPr2PS)2}H] (9) compounds, respectively. Formal potentials for Ru[N(R2PQ)2] complexes have been determined. The structures for complexes 1, 1a, 5, 6, 8 and 9 have been established by X-ray crystallography. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2009)
Co-reporter:Ngai-Man Lam, Xiao-Yi Yi, Chun-Sing Lai, Wai-Man Cheung, Qian-Feng Zhang, Ian D. Williams, Wa-Hung Leung
Inorganica Chimica Acta 2009 Volume 362(Issue 15) pp:5190-5194
Publication Date(Web):1 December 2009
DOI:10.1016/j.ica.2009.09.029
Treatment of [Bun4N][Ru(N)Cl4] with Na(OR) afforded [Bun4N][Ru(N)(OR)4] (R = C6F5 (1), C6F4H (2), C6Br5 (3)), whereas that with [Bun4N][Os(N)Cl4] gave [Bun4N][Os(N)(OR)3Cl] (R = C6F5 (4), C6F4H (5), C6Br5 (6)). Treatment of [Bun4N][M(N)Cl4] with Na(SC6F4H) and Na(Sxyl) (xyl = 2,6-dimethylphenyl) afforded [Bun4N][M(N)(SC6F4H)4] (M = Ru (7), Os (8)) and [Bun4N][M(N)(Sxyl)4] (M = Ru (9), Os (10)), respectively. The crystal structures of compounds 1, 6 and 9 have been determined.Treatment of [Bun4N][Ru(N)Cl4] with Na(OR) afforded [Bun4N][Ru(N)(OR)4] (R = C6F5 (1), C6F4H (2), C6Br5 (3)), whereas that with [Bun4N][Os(N)Cl4] gave [Bun4N][Os(N)(OR)3Cl] (R = C6F5 (4), C6F4H (5), C6Br5 (6)). Treatment of [Bun4N][M(N)Cl4] with Na(SC6F4H) and Na(Sxyl) (xyl = 2,6-dimethylphenyl) afforded [Bun4N][M(N)(SC6F4H)4] (M = Ru (7), Os (8)) and [Bun4N][M(N)(Sxyl)4] (M = Ru (9), Os (10)), respectively.
Co-reporter:Xiao-Yi Yi, Qian-Feng Zhang, Ian D. Williams, Wa-Hung Leung
Journal of Organometallic Chemistry 2009 694(26) pp: 4256-4260
Publication Date(Web):
DOI:10.1016/j.jorganchem.2009.08.036
Co-reporter:Ka-Wang Chan, Enrique Kwan Huang, Ian D. Williams and Wa-Hung Leung
Organometallics 2009 Volume 28(Issue 19) pp:5794-5801
Publication Date(Web):September 10, 2009
DOI:10.1021/om900598j
Treatment of Ru(dtbpy)(NO)Cl3 (dtbpy = 4,4′-di-tert-butyl-2,2′-bipyridyl) (1) with Me3SiCH2MgCl afforded the trialkyl compound mer-Ru(dtbpy)(NO)(CH2SiMe3)3 (2), which exhibits νNO at 1741 cm−1 in the IR spectrum. The solid-state structure of 2 shows a mer arrangement for the three alkyl groups and that the nitrosyl is trans to dtbpy. Protonation of 2 with HX afforded the dialkyl compounds cis,cis-Ru(dtbpy)(CH2SiMe3)(NO)X (X = Cl (3), OTs (4)), in which X is trans to an alkyl group. Treatment of 3 with AgOTf (OTf− = triflate) afforded cis,cis-Ru(dtbpy)(CH2SiMe3)2(NO)(OTf) (5), which reacted with amines RNH2 to give the adducts cis,cis-[Ru(dtbpy)(CH2SiMe3)2(NO)(NH2R)][OTf] (R = meistyl (6), 4-tol (7)). Substitution of 5 with NaOR led to the isolation of cis,trans-Ru(dtbpy)(CH2SiMe3)2(NO)(OR) (R = Ph (8), SiMe3 (9), SiPh3 (10)), in which the nitrosyl is trans to OR−, whereas that with NaSR gave cis,cis-Ru(dtbpy)(CH2SiMe3)2(NO)(SR) (R = 2,6-Me2C6H4 (11), SiPh3 (12)). Treatment of 5 with K[OsO3N] afforded the bimetallic complex cis,cis-Ru(dtbpy)(CH2SiMe3)2(NO)(NOsO3) (13), containing an unsymmetrical Os(VIII)≡N−Ru(II) bridge. The crystal structures of 2−5, 7−10, 12, and 13 have been determined.
Co-reporter:Xiao-Yi Yi, Herman H. Y. Sung, Ian D. Williams and Wa-Hung Leung
Chemical Communications 2008 (Issue 28) pp:3269-3271
Publication Date(Web):11 Jun 2008
DOI:10.1039/B800176F
Interaction of [Ce(LOEt)2(NO3)2] (LOEt− = [Co(η5-C5H5){P(O)(OEt)2}3]−) with (NH4)6[Mo7O24] in water affords the cerium(IV)-containing oxomolybdenum cluster [H4(CeLOEt)6Mo9O38], which exhibits a unique Ce6Mo9O38 core structure.
Co-reporter:Wai-Man Cheung, Ho-Yuen Ng, Ian D. Williams and Wa-Hung Leung
Inorganic Chemistry 2008 Volume 47(Issue 10) pp:4383-4391
Publication Date(Web):April 9, 2008
DOI:10.1021/ic800018d
Treatment of Ru(PPh3)3Cl2 with K(tpip) (tpip− = [N(Ph2PO)2]−) afforded Ru(tpip)(PPh3)2Cl (1), which reacted with 4-t-Bu-C6H4CN, SO2(g), and NH3(g) to give Ru(tpip)(PPh3)2Cl(4-t-BuC6H4CN) (2), Ru(tpip)(PPh3)2Cl(SO2) (3), and fac-[Ru(NH3)3(PPh3)2Cl][tpip] (4), respectively. Reaction of [Ru(CO)2Cl2]x with K(tpip) in refluxing tetrahydrofuran (THF) led to isolation of the K/Ru bimetallic compound K2Ru2(tpip)4(CO)4Cl2 (5). Photolysis of cis-Ru(tpip)2(NO)Cl in MeCN and wet CH2Cl2 afforded cis-Ru(tpip)2(MeCN)Cl (6) and cis-Ru(tpip)2(H2O)Cl (7), respectively. Refluxing 6 in neat THF yielded Ru(tpip)2(THF)Cl (8). Treatment of Ru(CHR)Cl2(PCy3)2 (Cy = cyclohexyl) with [Ag(tpip)]4 afforded cis-Ru(tpip)2(CHR)(PCy3) [R = Ph (9), OEt (10)]. Complex 9 is capable of catalyzing oxidation of alcohols and olefins with N-methylmorpholine N-oxide and iodosylbenzene, respectively. The crystal structures of 2−7 and 9 were determined.
Co-reporter:Ka-Wang Chan;Yiu-Keung Sau;Qian-Feng Zhang;Wai-Yeung Wong;Ian D. Williams
European Journal of Inorganic Chemistry 2008 Volume 2008( Issue 28) pp:4353-4359
Publication Date(Web):
DOI:10.1002/ejic.200800460
Abstract
Treatment of [Ir(dtbpy){CH2CMe2Cc6H4(Ir–Cc)}(C6H4tBu-2)] (1) (dtbpy = 4,4′-di-tert-butyl-2,2′-bipyridyl) with the dichalcogenides R2Q2 in refluxing toluene afforded the chalcogenolate-bridged dinuclear complexes [Ir(dtbpy) {CH2CMe2Cc6H4(Ir–Cc)}]2(μ-QR)2 [RQ = pTolS (2), PhSe (3)]. Similarly, heating a solution of [Rh(dtbpy){CH2CMe2Cc6H4(Ir–Cc)}(CH2CMe2Ph)] and p-tolyl sulfide in toluene at reflux gave [Rh(dtbpy){CH2CMe2Cc6H4(Ir–Cc)}]2(μ-SpTol)2 (4). Treatment of [Ir(dtbpy)(CH2CMe2Ph)Cl]2(μ-Cl)2 with Na(Sxyl) (xyl = 2,6-dimethylphenyl) and Na2(S∧S) afforded [Ir(dtbpy)(CH2CMe2Ph)(Sxyl)2]2 (5) and [Ir(dtbpy)(CH2CMe2Ph)(S∧S)]2 {S∧S2– = maleonitriledithiolate (6), toluene-3,4-dithiolate (7), benzene-1,2-dithiolate (8)}. Oxidation of compound 8 with AgOTf (OTf– = triflate) resulted in dimerization of the bdt2– ligand by S–S bond formation and the isolation of [Ir2(dtbpy)2(CH2Me2Ph)2{(bdt)2}][OTf]2 (9). The solid-state structures of compounds 2, 3, 4, 7, and 9 were determined. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2008)
Co-reporter:Wa-Hung Leung, Qian-Feng Zhang, Xiao-Yi Yi
Coordination Chemistry Reviews 2007 Volume 251(17–20) pp:2266-2279
Publication Date(Web):September 2007
DOI:10.1016/j.ccr.2006.11.019
The Kläui oxygen tripodal ligands [(η5-C5H5)Co{P(O)(OR)2}3]− (LOR− where R = alkyl group), which have been recognized as oxygen analogues of cyclopentadienyl, can form stable complexes with a range of main group and transition metal ions. This review reports on the recent developments in the coordination and organometallic chemistry of the Kläui tripodal ligands. Special attention will be paid to polynuclear M-LOEt (M = Ti, Zr) oxo and hydroxo compounds that may serve as models for group 4 metal aqua ions.
Co-reporter:Wai-Man Cheung, Chui-Ying Lai, Qian-Feng Zhang, Wai-Yeung Wong, Ian D. Williams, Wa-Hung Leung
Inorganica Chimica Acta 2006 Volume 359(Issue 9) pp:2712-2720
Publication Date(Web):1 June 2006
DOI:10.1016/j.ica.2005.10.021
Treatment of [MCl(CO)(PPh3)2] with K[N(R2PQ)2] afforded [M{N(Ph2PQ)2}(CO)(PPh3)] (M = Ir, Rh; Q = S, Se). The IR C=O stretching frequencies for [M(CO)(PPh3){N(Ph2PQ)2}] were found to decrease in the order S > Se. Treatment of [M(COD)Cl]2 with K[N(Ph2PQ)2] afforded [M(COD){N(Ph2PQ)2}] (COD = 1,5-cyclooctadiene; M = Ir, Rh; Q = S, Se). Treatment of [Ir(ol)2Cl] with K[N(Pr2iPQ)2] afforded [Ir(ol)2{N(Pr2iPQ)2}]2 (ol = cyclooctene COE, C2H4; Q = S, Se). Oxidative addition of [Ir(CO)(PPh3){N(Ph2PS)2}] and [Ir(COD){N(Ph2PS)2}] with HCl afforded [Ir(H)(Cl)(CO)(PPh3){N(Ph2PS)2}] and trans-[Ir(H)(Cl)(COD){N(Ph2PS)2}], respectively. Oxidative addition of [Ir(CO)(PPh3){N(Ph2PS)2}] with MeI afforded [Ir(Me)(I)(CO)(PPh3){N(Ph2PS)2}]. Treatment of [Ir(COE)2Cl]2 with K[N(R2PO)2] afforded [Ir(COE)2{N(Ph2PO)2}] that reacted with MeOTf (OTf = triflate) to give [Ir{N(Ph2PO)2}(COE)2(Me)(OTf)]. The crystal structures of [Ir(CO)(PPh3){N(Ph2PS)2}], [M(COD){N(Ph2PS)2}] (M = Ir, Rh), [Ir(ol)2{N(Pr2iPS)2}](ol = COE, C2H4), trans-[Ir(H)(Cl)(COD){N(Ph2PS)2}], and [Ir(COE)2{N(Ph2PO)2}] have been determined.Ir(I) and Rh(I) dichalcogenoimidodiphosphinato complexes of the types [M(CO)(PPh3){N(Ph2PQ)2}], [M(COD){N(Ph2PQ)2}], and [Ir(ol)2{N(Pr2iPQ)2}](M=Ir,Rh;Q=O,S,Se;ol=cyclooctene,C2H4) have been synthesized. Oxidative addition of the Ir(I) dichalcogenoimidodiphosphinato complexes with MeI and HCl has been studied.
Co-reporter:Xiao-Yi Yi, Gary K.Y. Ng, Ian D. Williams, Wa-Hung Leung
Inorganica Chimica Acta 2006 Volume 359(Issue 11) pp:3581-3588
Publication Date(Web):1 August 2006
DOI:10.1016/j.ica.2006.02.036
Treatment of [Ti(OPri)2Cl2] with K(tpip) (tpip− = [N(PPh2O)2]−) followed by chlorination with HCl afforded cis-[Ti(tpip)2Cl]2 (1). Reduction of 1 with Na/Hg in THF gave [Ti(tpip)3] (2), which could also be prepared from [TiCl3(THF)3] and K(tpip). Recrystallization of [V(O)(tpip)2] (3) from CH2Cl2–Et2O in air afforded trinuclear [{V(O)}3(μ-tpip)3(μ-O)3] (4). Treatment of [Cr(NBut)2Cl2] and [Cr(NBut)Cl3(dme)] (dme = 1,2-dimethoxyethane) with [Ag(tpip)]4 led to isolation of [Cr(tpip)3] (6) and [Cr(NBut)(tpip)2Cl] (7), respectively. The Ti- and V-tpip complexes are capable of catalyzing oxidation of sulfides with tert-butyl hydroperoxide and H2O2. The crystal structures of 1, 2, and 4 have been determined.Treatment of [Ti(OPri)2Cl2] with K(tpip) (tpip− = [N(PPh2O)2]−) followed by chlorination with HCl afforded cis-[Ti(tpip)2Cl2]. Recrystallization of [V(O)(tpip)2] from CH2Cl2–Et2O in air afforded trinuclear [(VO)3(μ-tpip)(μ-O)]3. Treatment of [Cr(NBut)Cl3(dme)] with [Ag(tpip)]4 afforded [Cr(NBut)(tpip)2Cl]. The Ti- and V-tpip complexes can catalyze oxidation of sulfides with tert-butyl hydroperoxide and H2O2.
Co-reporter:Wai-Man Cheung, Qian-Feng Zhang, Ian D. Wiliams, Wa-Hung Leung
Inorganica Chimica Acta 2006 Volume 359(Issue 3) pp:782-788
Publication Date(Web):1 February 2006
DOI:10.1016/j.ica.2005.04.031
Treatment of [Cp*RuCl2]x (Cp* = η5-C5Me5) with K[N(Ph2PS)2] afforded [Cp*Ru{N(Ph2PS)2}Cl] (1). Reduction of 1 with Li[BEt3H] gave the 16-electron half-sandwich Ru(II) complex [Cp*Ru{N(Ph2PS)2}] (2). Complexes 1 and 2 have been characterized by X-ray crystallography. The Ru–Cp*(centroid) and average Ru–S distances in 1 are 1.827 and 2.3833(5) Å, respectively. The corresponding bond distances in 2 are 1.739 and 2.379(1) Å. Treatment of 2 with 2-electron ligands L afforded the adducts [Cp*Ru{N(Ph2PS)2}L] (L = CO (3), 2,6-Me2C6H4NC (4), MeCO2CCCO2Me (5)). Oxidation of 2 with tetramethylthiuram disulfide gave the Ru(IV) complex [Cp*Ru{S2CNMe2}2][N(Ph2PS)2] (6). The Ru–Cp*(centroid) and average Ru–S distances in 6 are 1.897 and 2.387(1) Å, respectively.Reduction of [Cp*Ru{N(Ph2PS)2}Cl] (Cp* = η5-C5Me5) with Li[BEt3H] gives the 16-electron unsaturated Ru(II) complex [Cp*Ru{N(Ph2PS)2}], which exhibits an approximately perpendicular arrangement between the Cp* ring and the Ru-S-S′ plane. [Cp*Ru{N(Ph2Ps)2}] reacts with 2-electron ligands L to give the 18-electron adducts [Cp*Ru{N(Ph2PS)2}(L)] (L = CO, isocyanide and alkyne).
Co-reporter:Yiu-Keung Sau Dr.;Hung-Kay Lee Dr.;Ian D. Williams Dr. Dr.
Chemistry - A European Journal 2006 Volume 12(Issue 36) pp:
Publication Date(Web):22 SEP 2006
DOI:10.1002/chem.200600562
Treatment of IrCl3⋅x H2O with one equivalent of 4,4′-di-tert-butyl-2,2′-bipyridyl (dtbpy) in N,N-dimethylformamide (dmf) afforded [IrCl3(dmf)(dtbpy)] (1). Alkylation of 1 with Me3SiCH2MgCl resulted in CSi cleavage of the Me3SiCH2 group and formation of the IrIII silyl dialkyl compound [Ir(CH2SiMe3)(dtbpy)(Me)(SiMe3)] (2), which reacted with tBuNC to afford [Ir(tBuNC)(CH2SiMe3)(dtbpy)(Me)(SiMe3)] ([2(tBuNC)]). Reaction of 2 with phenylacetylene afforded dimeric [{Ir(CCPh)(dtbpy)(SiMe3)}2(μ-CCPh)2] (3), in which the bridging PhCC− ligands are bound to Ir in a μ-σ:π fashion. Alkylation of 1 with PhMe2CCH2MgCl afforded the cyclometalated compound [Ir(dtbpy)(CH2CMe2C6H4)(2-C6H4CMe3)] (4), which features an agostic interaction between the Ir center and the 2-tert-butylphenyl ligand. The cyclic voltammogram of 4 in CH2Cl2 shows a reversible IrIV–IrIII couple at about 0.02 V versus ferrocenium/ferrocene. Oxidation of 4 in CH2Cl2 with silver triflate afforded an IrIV species that exhibits an anisotropic electron paramagnetic resonance (EPR) signal in CH2Cl2 glass at 4 K with g∥=2.430 and g⊥=2.110. Protonation of 4 with HCl and p-toluenesulfonic acid (HOTs) afforded [{Ir(dtbpy)(CH2CMe2Ph)Cl}2(μ-Cl)2] (5) and [Ir(dtbpy)(CH2CMe2Ph)(OTs)2] (6), respectively. Reaction of 5 with Li[BEt3H] gave the cyclometalated complex [{Ir(dtbpy)(CH2CMe2C6H4)}2(μ-Cl)2] (7). Reaction of 4 with tetracyanoethylene in refluxing toluene resulted in electrophilic substitution of the iridacycle by C2(CN)3 with formation of [Ir(dtbpy)(CH2CMe2C6H3{4-C2(CN)3})(2-C6H4CMe3)] (8). Reaction of 4 with diethyl maleate in refluxing toluene gave the iridafuran compound [Ir(dtbpy)(CH2CMe2C6H4){κ2(C,O)-C(CO2Et)CH(CO2Et)}] (9). Treatment of 9 with 2,6-dimethylphenyl isocyanide (xylNC) led to cleavage of the iridafuran ring and formation of [Ir(dtbpy)(CH2CMe2C6H4){C(CO2Et)CH(CO2Et)}(xylNC)] (10). Protonation of 9 with HBF4 afforded the dinuclear neophyl complex [(Ir(dtbpy)(CH2CMe2Ph){κ2(C,O)-C(CO2Et)CH(CO2Et)})2][BF4]2 (11). The solid-state structures of complexes 2–5 and 8–11 have been determined.
Co-reporter:Qian-Feng Zhang;Ka-Man Cheung;Ian D. Williams
European Journal of Inorganic Chemistry 2005 Volume 2005(Issue 23) pp:
Publication Date(Web):25 OCT 2005
DOI:10.1002/ejic.200500420
Transmetalation of Hg(ptpy)2 [Hptpy = 2-(4-tolylpyridine) with Cp*Ru(NO)Cl2 (Cp* = η5-C5Me5)] gave [Cp*Ru(NO)(ptpy)]2[Hg2Cl6] ([1]2·Hg2Cl6) whereas that with [Cp*RuCl2]x gave the dinuclear RuII–RuIV compound [Cp*Ru(μ-η6:η2-ptpy)RuCl2Cp*][Hg2Cl6] (2). Treatment of Ru(3-phenylindenylid-1-ene)Cl2(PPh3)2 with Hg(ptpy)2 resulted in coupling of ptpy with the 3-phenylidenylid-1-ene ligand, and the formation of Ru(Ph-ind-ptpy)(PPh3)Cl {Ph-ind-tpy = 3-phenyl-1-[2-(4-toyl)pyridyl]indenyl} (3), in which the chelated [Ph-ind-tpy]– ligand binds to Ru through the η5-indenyl ring and the pendant pyridyl group. Treatment of [Ru(CO)2Cl2]n with [Hg(ptpy)Cl]2 afforded [Ru(ptpy)(CO)2]2(μ-Cl)2 (8). Irradiation of cis-[Ru(bzq)2(CO)2] (Hbzq = benzo[h]quinoline) with UV light in MeCN afforded cis-[Ru(bzq)2(CO)(MeCN)] (9). Photolysis of cis-[Ru(bzq)2(CO)2] in THF in the presence of PPh3 and pyridine (py) afforded cis-[Ru(bzq)2(CO)(L)] [L = PPh3 (10), py (11)]. The crystal structures of complexes 1–3, 8, and 10 have been determined. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2005)
Co-reporter:Ka-Man Cheung, Qian-Feng Zhang, Wing-Leung Mak, Herman H.Y. Sung, Ian D. Williams, Wa-Hung Leung
Journal of Organometallic Chemistry 2005 Volume 690(Issue 2) pp:253-260
Publication Date(Web):17 January 2005
DOI:10.1016/j.jorganchem.2004.09.018
Treatment of Ni(HP1) (H3P1 = meso-5-[4′-(2″-pyridyl)phenyl]-10,15,20-triphenyporphyrin) with K2[PdCl4] in EtOH afforded [Pd{Ni(P1)}]2(μ-Cl)2 that reacted with NaS2CNEt2 to give Pd(S2CNEt2)[Ni(P1)]. Reaction of Ni(HP1) with [Ir(H)2(PPh3)2(Me2CO)2][BF4] afforded Ir(H)Cl(PPh3)2[Ni(P1)]. The crystal structures of Pd(S2CNEt2)[Ni(P1)] and Ir(H)(Cl)(PPh3)2[Ni(P1)] have been determined.Ni(HP1) (H3P1 = meso-5-[4′-(2″-pyridyl)phenyl]-10,15,20-triphenylporphyrin) reacts with [PdCl4]2−/NaS2CNEt2 and [Ir(H)2(PPh3)2(Me2CO)2][BF4] to give the bimetallic cyclometalated porphyrin complexes Pd(S2CNEt2)[Ni(P1)] and Ir(H)Cl(PPh3)2[Ni(P1)], respectively, which have been characterized by X-ray crystallography.
Co-reporter:Ka-Man Cheung, Qian-Feng Zhang, Ka-Wang Chan, Michael H.W. Lam, Ian D. Williams, Wa-Hung Leung
Journal of Organometallic Chemistry 2005 Volume 690(Issue 12) pp:2913-2921
Publication Date(Web):15 June 2005
DOI:10.1016/j.jorganchem.2005.03.013
Treatment of [Ir(ppy)2(μ-Cl)]2 and [Ir(ppy)2(dtbpy)][OTf] (ppy = 2-(2′-pyridyl)phenyl; dtbpy = 4,4′-di-tert-butyl-2,2′-bipyridine; OTf = triflate) with pyridinium tribromide in the presence of Fe powder led to isolation of [Ir(4-Br-ppy)(μ-Br)]2 (1) and [Ir(4-Br-ppy)2(dtbpy)][OTf] (2), respectively. Pd-catalyzed cross-coupling of 2 with RB(OH)2 afforded [Ir(4-R-ppy)2(dtbpy)][OTf] (R = 4′-FC6H4 (3)), 4′-PhC6H4 (4), 2′-thienyl (5), 4′-C6H4CH2OH (6). Treatment of 4 with B2(pin)2 (pin = pinacolate) afforded [Ir{4-(pin)B-ppy}2(dtbpy)][OTf] (7). The alkynyl complexes [Ir(4-PhCC-ppy)2(dtbpy)][OTf] (8) and [Ir{4-Me2(OH)CC-ppy}(4-Br-ppy)(dtbpy)][OTf] (9) were prepared by cross-coupling of 2 with PhCCSnMe3 and Me2C(OH)CCH, respectively. Ethynylation of [Ir(fppy)2(dtbpy)][OTf] (fppy = 5-formyl-2-(2′-pyridyl)phenyl) with Ohira’s reagent MeCOC(N2)P(O)(OEt)2 afforded [Ir{5-HCC-ppy}2(dtbpy)][OTf] (10). The solid-state structures of 2, 5, 7, and 10 have been determined.The arylated Ir(III) cyclometalated complexes [Ir(4-R-ppy)2(dtbpy)][OTf] (ppy = 2-(2′-pyridyl)phenyl, dtbpy = 4,4′-di-tert-butyl-2,2′-bipyridine, OTf = triflate) have been synthesized by cross-coupling of the bromo-substituted Ir(III) cyclometalated complex [Ir(4-Br-ppy)2(dtbpy)][OTf] with aryl boronic acids RB(OH)2.
Co-reporter:Qian-Feng Zhang Dr.;Tony C. H. Lam Dr.;Xiao-Yi Yi;Eddie Y. Y. Chan Dr.;Wai-Yeung Wong Dr.;Herman H. Y. Sung Dr.;Ian D. Williams Dr. Dr.
Chemistry - A European Journal 2005 Volume 11(Issue 1) pp:
Publication Date(Web):10 NOV 2004
DOI:10.1002/chem.200400853
Treatment of titanyl sulfate in about 60 mM sulfuric acid with NaLOEt (LOEt−=[(η5-C5H5)Co{P(O)(OEt)2}3]−) afforded the μ-sulfato complex [(LOEtTi)2(μ-O)2(μ-SO4)] (2). In more concentrated sulfuric acid (>1 M), the same reaction yielded the di-μ-sulfato complex [(LOEtTi)2(μ-O)(μ-SO4)2] (3). Reaction of 2 with HOTf (OTf=triflate, CF3SO3) gave the tris(triflato) complex [LOEtTi(OTf)3] (4), whereas treatment of 2 with Ag(OTf) in CH2Cl2 afforded the sulfato-capped trinuclear complex [{(LOEt)3Ti3(μ-O)3}(μ3-SO4){Ag(OTf)}][OTf] (5), in which the Ag(OTf) moiety binds to a μ-oxo group in the Ti3(μ-O)3 core. Reaction of 2 in H2O with Ba(NO3)2 afforded the tetranuclear complex (LOEt)4Ti4(μ-O)6 (6). Treatment of 2 with [{Rh(cod)Cl}2] (cod=1,5-cyclooctadiene), [Re(CO)5Cl], and [Ru(tBu2bpy)(PPh3)2Cl2] (tBu2bpy=4,4′-di-tert-butyl-2,2′-dipyridyl) in the presence of Ag(OTf) afforded the heterometallic complexes [(LOEt)2Ti2(O)2(SO4){Rh(cod)}2][OTf]2 (7), [(LOEt)2Ti(O)2(SO4){Re(CO)3}][OTf] (8), and [{(LOEt)2Ti2(μ-O)}(μ3-SO4)(μ-O)2{Ru(PPh3)(tBu2bpy)}][OTf]2 (9), respectively. Complex 9 is paramagnetic with a measured magnetic moment of about 2.4 μB. Treatment of zirconyl nitrate with NaLOEt in 3.5 M sulfuric acid afforded [(LOEt)2Zr(NO3)][LOEtZr(SO4)(NO3)] (10). Reaction of ZrCl4 in 1.8 M sulfuric acid with NaLOEt in the presence Na2SO4 gave the μ-sulfato-bridged complex [LOEtZr(SO4)(H2O)]2(μ-SO4) (11). Treatment of 11 with triflic acid afforded [(LOEt)2Zr][OTf]2 (12), whereas reaction of 11 with Ag(OTf) afforded a mixture of 12 and trinuclear [{LOEtZr(SO4)(H2O)}3(μ3-SO4)][OTf] (13). The ZrIV triflato complex [LOEtZr(OTf)3] (14) was prepared by reaction of LOEtZrF3 with Me3SiOTf. Complexes 4 and 14 can catalyze the Diels–Alder reaction of 1,3-cyclohexadiene with acrolein in good selectivity. Complexes 2–5, 9–11, and 13 have been characterized by X-ray crystallography.
Co-reporter:Man-Kit Lau, Ka-Man Cheung, Qian-Feng Zhang, Yinglin Song, Wing-Tak Wong, Ian D. Williams, Wa-Hung Leung
Journal of Organometallic Chemistry 2004 Volume 689(Issue 14) pp:2401-2410
Publication Date(Web):15 July 2004
DOI:10.1016/j.jorganchem.2004.04.033
Treatment of [M(Buppy)2Cl]2 (M=Ir (1), Rh (2); BuppyH=2-(4′-tert-butylphenyl)pyridine) with Na(Et2NCS2), K[S2P(OMe)2], and K[N(Ph2PS)2]2 afforded monomeric [Ir(Buppy)2(S∧S)] (S∧S=Et2NCS2 (3), S2P(OMe)2 (4), N(PPh2S)2 (5)) and [Rh(Buppy)2(S∧S)] (S∧S=Et2NCS2 (6), S2P(OMe)2 (7), N(PPh2S)2 (8)), respectively. Reaction of 1 with Na[N(PPh2Se)2] gave [Ir(Buppy)2{N(PPh2Se)2}] (9). The crystal structures of 3, 4, 7, and 8 have been determined. Treatment of 1 or 2 with AgOTf (OTf=triflate) followed by reaction with KSCN gave dinuclear [{M(Buppy)2}2(μ-SCN)2] (M=Ir (10), Rh (11)), in which the SCN− ligands bind to the two metal centers in a μ-S,N fashion. Interaction of 1 and 2 with [Et4N]2[WQ4] gave trinuclear heterometallic complexes [{Ir(Buppy)2}2(μ-WQ4)] (Q=S (12), Se (13)) and [{Rh(Buppy)2}2{(μ-WQ)4}] (Q=S (14), Se (15)), respectively. Hydrolysis of 12 led to formation of [{Ir(Buppy)2}2{W(O)(μ-S)2(μ3-S)}] (16) that has been characterized by X-ray diffraction.Teatment of [M(Buppy)2Cl]2 with bidentate sulfur ligands S∧S afforded the cyclometalated complexes [M(Buppy)2(S∧S)] (M=Ir or Rh; BuppyH=2-(4′-tert-butylphenyl)pyridine; S∧S=Et2NCS2, S2P(OMe)2, N(PPh2S)2). Interactions of [M(Buppy)2Cl]2 with [WQ4]2− (Q=S or Se) afforded the trinuclear heterometallic complexes [{M(Buppy)2}2(μ-WQ4)].
Co-reporter:Qian-Feng Zhang Dr.;Tony C. H. Lam Dr.;Eddie Y. Y. Chan Dr.;Samuel M. F. Lo Dr.;Ian D. Williams Dr.;Wa-Hung Leung Dr.
Angewandte Chemie 2004 Volume 116(Issue 13) pp:
Publication Date(Web):17 MAR 2004
DOI:10.1002/ange.200353298
Wasserlöslich und stabil: Die Behandlung von Zirconylnitrat mit dem tripodalen Kläui-Sauerstoffliganden in verdünnter Salpetersäure führt zu einer wasserlöslichen, vierkernigen hydroxoverbrückten ZrIV-Verbindung (siehe Bild; C grau, O rot, P lila, Co blau, Zr grün), die mit einem Phosphodiester zu einem ZrIV-Phosphat-Cubancluster reagiert.
Co-reporter:Qian-Feng Zhang Dr.;Tony C. H. Lam Dr.;Eddie Y. Y. Chan Dr.;Samuel M. F. Lo Dr.;Ian D. Williams Dr.;Wa-Hung Leung Dr.
Angewandte Chemie International Edition 2004 Volume 43(Issue 13) pp:
Publication Date(Web):17 MAR 2004
DOI:10.1002/anie.200353298
Water soluble and stable: The treatment of zirconyl nitrate with the Kläui tripodal oxygen ligand in dilute nitric acid gives a water-soluble tetranuclear hydroxo-bridged ZrIV compound (depicted, C gray; O red; P purple; Co blue; Zr green), which reacts with a phosphodiester to give a ZrIV phosphate cubane cluster.
Co-reporter:Wa-Hung Leung
European Journal of Inorganic Chemistry 2003 Volume 2003(Issue 4) pp:
Publication Date(Web):29 JAN 2003
DOI:10.1002/ejic.200390080
Organoimido groups are excellent spectator ligands for high-valent organometallic compounds due to their strong π-donating capability. Of interest are imidochromium complexes that are used as catalysts for olefin polymerization. This microreview provides an overview of the organometallic chemistry of high-valent imidochromium complexes. Synthetic routes to alkyl- and arylimido complexes of chromium in oxidation states VI−IV will be presented. The reactivity of imidochromium complexes including imido group transfer and cycloaddition will be described. The use of imidochromium complexes as catalysts for regioselective ring opening of epoxides will be discussed. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003)
Co-reporter:Qian-Feng Zhang, Yinling Song, Wai-Yeung Wong, Wa-Hung Leung and Xinquan Xin
Dalton Transactions 2002 (Issue 9) pp:1963-1968
Publication Date(Web):11 Apr 2002
DOI:10.1039/B110583N
Reaction of [NEt4]2[WSe4] with [Pd2(dppm)2Cl2] afforded the hexanuclear windmill-shaped compound [(WSe4)2Pd4(dppm)2] (1) {dppm = bis(diphenylphosphino)methane}. Treatment of [NEt4]2[WSe4] with [Pd(P∧P)Cl2] gave the dinuclear compounds [(WSe4)Pd(P∧P)] {P∧P = dppe, 1,2-bis(diphenylphosphino)ethane (2); dppp, 1,3-bis(disphenylphosphino)propane (3)}. The crystal structures of these heteroselenometallic W–Se–Pd compounds have been determined and their nonlinear optical properties were studied with an 8 ns pulsed laser at 532 nm. It was found that compounds 1–3
show predominantly nonlinear refraction and negligible nonlinear absorption. Compound 1 exhibits a considerable self-defocusing properties with the nonlinear refractivity (n2) value estimated to be −3.74 × 10−10 cm2 W−1 M−1. The optical limiting thresholds of compounds 1, 2 and 3 were determined to be ca. 3.1, 6.5 and 7.2 J cm−2, respectively.
Co-reporter:Qian-Feng Zhang, Yunying Niu, Wa-Hung Leung, Yinglin Song, Ian D. Williams and Xinquan Xin
Chemical Communications 2001 (Issue 12) pp:1126-1127
Publication Date(Web):31 May 2001
DOI:10.1039/B101929P
The self-assembly reaction of the monomeric nest-shaped
cluster
[NEt4]2[MoOS3Cu3I3]
1 or twin nest-shaped cluster
[NEt4]4[Mo2O2S6Cu
6I6] 2 with the bridging ligand 4,4′-bipyridine
(4,4′-bipy) gave a 2D polymeric cluster {[NEt4]-
[Mo2O2S6Cu6I3(4,4
′-bipy)5]·MeOH·H2O}
n 3, which exhibits a significant improvement of
optical limiting effect in its nonlinear optical properties relative to 1
or 2.
Co-reporter:Man-Kit Lau, Qian-Feng Zhang, Joyce L. C. Chim, Wing-Tak Wong and Wa-Hung Leung
Chemical Communications 2001 (Issue 16) pp:1478-1479
Publication Date(Web):23 Jul 2001
DOI:10.1039/B104075H
The osmium(IV) tetraaryl complex
[Os(C8H9)4] (C8H9 =
2,5-dimethylphenyl) reacts with pyridinium tribromide in the presence of Fe
powder to give [Os(C8H8Br)4], which
undergoes Suzuki coupling with arylboronic acids to afford a series of
homoleptic functionalised aryls of osmium(IV).
Co-reporter:Willetta Lai, Man-Kit Lau, Victor Chong, Wing-Tak Wong, Wa-Hung Leung, Nai-Teng Yu
Journal of Organometallic Chemistry 2001 Volume 634(Issue 1) pp:61-68
Publication Date(Web):13 September 2001
DOI:10.1016/S0022-328X(01)01097-X
Interactions of trans-[Rh(bpb)(CH3)(H2O)] (1) [bpb=1,2-bis(2-pyridinecarboxamido)benzene] with Lewis bases L afford the respective adducts trans-[Rh(bpb)(CH3)(L)], where L=4-substituted pyridine 4-Xpy (X=H (2), tBu (3), NMe2 (4) CN (5)), PMe2Ph (6) or benzimidazole (7). The structures of complexes 3 and 6 have been established by X-ray crystallography. The Rh–C distance in complex 6 (2.095(6) Å) is longer than that in complex 3 (2.02(1) Å), indicating that PMe2Ph has a stronger trans influence than 4-tBupy. The metal–carbon stretching frequencies for trans-[Rh(bpb)(CH3)(L)] and [M(TTP)(CH3)] [TTP=5,10,15,20-tetrakis(4-methylphenyl)porphyrin dianion; M=Rh, Ir, Ga, In] have been determined by near IR FT-Raman spectroscopy. Complex 1 exhibits ν(Rh–C) at 562 cm−1, which downshifts to 532 cm−1 upon deuteriation of the axial methyl group. Replacement of the aquo ligand in complex 1 with nitrogen ligands or phosphine resulted in downshift in ν(Rh–C). The ν(Rh–C) for trans-[Rh(bpb)(CH3)(L)] was found to decrease in the order L: PMe2Ph≫4-Xpy∼BzIm>H2O, consistent the order of trans influence of L. For [M(TTP)(CH3)] (M=Co, Rh, Ir, Ga, or In) the M–C force constant was found to decrease in the orders Ir>Rh>Co and Ga>In, consistent with the trends of metal–carbon bond strength for these metals. For trans-[Rh(bpb)(CH3)(4-Xpy)] and trans-[Rh(TTP)(CH3)(4-Xpy)], the ν(Rh–C) were found to be not very sensitive to the nature of X, suggesting that the electronic factors of the axial pyridine ligand do not have a significant effect on the Rh–C bonds for these rhodium alkyl complexes.The metal–carbon stretching frequencies for trans-[Rh(bpb)(CH3)(L)] [bpb=1,2-bis(2-pyridinecarboxamido)benzene; L=4-substituted pyridine, benzimidazole or PMe2Ph], [M(TTP)(CH3)] (M=Rh, Ir, Ga, In) and trans-[Rh(TTP)(CH3)(4-Xpy)] [TTP=5,10,15,20-tetrakis(4-methylphenyl)porphyrin dianion] have been determined by FT-Raman spectroscopy. The effects of metal substitution and axial ligand on the metal–carbon stretching frequencies for these complexes have been investigated.
Co-reporter:Qian-Feng Zhang, Kwok-Kin Lau, Wai-Yeung Wong, Wa-Hung Leung
Inorganica Chimica Acta 2001 Volume 325(1–2) pp:125-129
Publication Date(Web):3 December 2001
DOI:10.1016/S0020-1693(01)00652-1
Co-reporter:Wa-Hung Leung, Eddie Y. Y. Chan, Tracy C. Y. Lai and Wing-Tak Wong
Dalton Transactions 2000 (Issue 1) pp:51-56
Publication Date(Web):24 Dec 1999
DOI:10.1039/A906618G
Interaction of [ReNCl3(PPh3)2] or [ReOCl2(PPh3)3] with NaLOEt (LOEt = [Co(η5-C5H5){PO(OEt)2}3]) afforded [ReLOEtN(PPh3)Cl] 1 and [ReLOEtOCl2] 2, respectively. Reaction of 1 with AgBF4 gave the nitridorhenium(VI) complex [ReLOEtN(PPh3)Cl]BF41·BF4, which has a μeff of 1.8 μB. Treatment of 1 with MeOSO2CF3, PhCH2Br or [Ph3C]BF4 afforded the respective organoimido species [ReLOEt(NMe)(PPh3)Cl][CF3SO3] 3, [ReLOEt(NCH2Ph)(PPh3)Cl]Br 4, and [ReLOEt(NCPh3)(PPh3)Cl] 5. Reaction of 1 with [Au(PPh3)(CF3SO3)], [Ru(Et2dtc)(PPh3)2(CO)(CF3SO3)], or [ReMeO3] yielded the bimetallic nitrido complexes [Au(PPh3){NReLOEt(PPh3)Cl}][CF3SO3] 6, [Ru(Et2dtc)(PPh3)(H2O)(CO){NReLOEt(PPh3)Cl}][CF3SO3] 7 or [ReMeO3{NReLOEt(PPh3)Cl}] 8, respectively. Treatment of [NBu4n][OsNCl4] with NaLOEt gave [OsLOEtNCl2] 9. The average Os–O, Os–Cl and Os–N distances in 9 are 2.066, 2.289 and 2.58(1) Å, respectively. Reaction of 9 with PPh3 afforded the osmium(IV) phosphoran iminate species [OsLOEt(NPPh3)Cl2] 10, which has a μeff of 2.0 μB. The average Os–O, Os–Cl and Os–N distances in 10 are 2.099, 2.342, 1.893(5) Å, respectively, the Os–N–P angle being 137.5(3)°. The formal potentials of the LOEt–Re and –Os complexes have been determined by cyclic voltammetry. On the basis of the ReVI–ReV formal potential, the π-donor strength was found to decrease in the order N3− > [NAu(PPh3)]2− > NMe2−.
Co-reporter:Wa-Hung Leung, Hegen Zheng, Hegen Zheng, Joyce L. C. Chim, Joe Chan, Wing-Tak Wong and Ian D. Williams
Dalton Transactions 2000 (Issue 3) pp:423-430
Publication Date(Web):14 Jan 2000
DOI:10.1039/A907753G
Reactions of [Ru(PPh3)3Cl2], [Ru(CO)2Cl2]x, or [Ru(dmso)4Cl2] (dmso = dimethyl sulfoxide) with KLR [LR = N(SPR2)2, R = Ph or Pri] afforded [Ru(LR)2(PPh3)] (R = Ph 1 or Pri2), cis-[Ru(LR)2(CO)2] (L = Ph 3 or Pri4), or cis-[Ru(LPh)2(dmso)2] 5, respectively. The crystal structures of complexes 1 and 2 have been determined. They show weak agostic interaction between Ru and LR with calculated Ru⋯H–C separations of 3.37 and 2.91 Å, respectively. The Ru–P and average Ru–S distances in 1 are 2.218(1) and 2.400 Å, respectively. The corresponding bond lengths for 2 are 2.210(2) and 2.404 Å. Treatment of 2 with ButNC afforded trans-[Ru(LPr)2(ButNC)2] 6, the average Ru–S and Ru–C distances of which are 2.453 and 1.990(3) Å, respectively. Reaction of RuCl3 with KLR in methanol gave the homoleptic complexes [Ru(LR)3] (L = Ph 7 or Pri8). The average Ru–S distance and S–Ru–S angle in 7 are 2.414 Å and 97.41°, respectively. While complex 1 reacts with pyridine (py) to give [Ru(LPh)2(PPh3)(py)] 9, reaction of 2 with py led to isolation of structurally characterised [Ru(LPr)2(SO)] 10. The Ru–S(O) and S–O bond lengths in 10 are 2.0563(11) and 1.447(3) Å, respectively, the Ru–S–O angle being 125.5(2)°. Treatment of 1 with SO2 afforded structurally characterised cis-[Ru(LPh)2(PPh3)(SO2)] 11. The SO2 ligand binds to Ru in 11 in a η1-S mode and the Ru–S(O) distance is 2.140(4) Å. Complex 2 reacted with SO2 to give the μ-sulfato-bridged ruthenium(III) dimer [{Ru(LPr)(PPh3)}2(μ-SO4)2] 12, which has been characterised by X-ray crystallography. The Ru–P and average Ru–S and Ru–O distances in 12 are 2.294(2), 2.321 and 2.133 Å, respectively. Complex 1 is capable of catalysing hydrogenation of styrene in the presence of Et3N presumably via a ruthenium hydride intermediate.
Co-reporter:Qian-Feng Zhang, Kwok-Kin Lau, Joyce L. C. Chim, Terry K. T. Wong, Wing-Tak Wong, Ian D. Williams and Wa-Hung Leung
Dalton Transactions 2000 (Issue 17) pp:3027-3033
Publication Date(Web):08 Aug 2000
DOI:10.1039/B003798M
Reactions of trans-K2[OsVIO2(OH)4] with 2 equivalents of HN(QPR2)2 yielded the dioxoosmium(VI) complexes trans-[OsO2{N(QPR2)2}2] (Q = S, R = Ph 1 or Pri2; Q = Se, R = Ph 3). Complexes 1–3 have been characterised by X-ray crystallography. The Os–O distances in 1–3 are 1.739, 1.734 and 1.748 Å, respectively. trans-[OsN{N(QPR2)2}2Cl] (R = Pri, Q = S; R = Ph, Q = Se) were obtained by reactions of [NBu4n][OsNCl4] with K[N(QPR2)2]. Treatment of [OsN{N(SPPh2)2}2][BF4] with [NBu4n][OsO3N] resulted in formation of a μ-nitrido OsVIII–OsVI complex [OsN{N(SPPh2)2}2(NOsO3)], in which the [NOsO3]− is trans to the terminal nitride ligand. The OsVI–N, OsVI–N(Os) and OsVIII–N distances are 1.617(12), 2.318(11), and 1.719(11) Å, respectively; the Os(1)–N(4)–Os(2) angle being 159.2(7)°. Treatment of [OsN{N(SPPh2)2}2][BF4] with [NBu4n][ReO4] or [NBu4n]2[M6O19] gave heterometallic μ-oxo complexes trans-[OsN{N(SPPh2)2}2(OReO3)] or trans-[{OsN[N(SPPh2)2]2}2(M6O19)] (M = Mo or W), respectively. Reaction of [NH4]2[OsCl6] with K[N(SPPh2)2] in the presence of PPh3 or treatment of 3 with C6F5SH led to isolation of the osmium(III) homoleptic complexes [Os{N(SPR2)2}3] (R = Pri or Ph). The geometry around Os in the latter is pseudo octahedral, and the average S–Os–S angle and average Os–S distance are 96.06(5)° and 2.450 Å, respectively. Osmium(III) phosphoraniminate complexes [Os(NPMePh2)(PMePh2){N(SPPh2)2}2] and trans-[Os(NPPh3)(PPh3){N(SePPh2)2}2] were prepared by the respective nitridoosmium(VI) complex with PMePh2 or PPh3. Reaction of complex 1 or 2 with hydrazine hydrate afforded air-sensitive osmium(II) dinitrogen species, presumably [Os{N(SPR2)2}2(N2)] (R = Ph or Pri), which exhibit IR ν(N2) at 2060 and 2040 cm−1, respectively.
Co-reporter:Hegen Zheng, Wa-Hung Leung, Joyce L.C Chim, Willetta Lai, Chong-Ho Lam, Ian D Williams, Wing-Tak Wong
Inorganica Chimica Acta 2000 Volume 306(Issue 2) pp:184-192
Publication Date(Web):21 August 2000
DOI:10.1016/S0020-1693(00)00169-9
Interaction of [Ru(Co)H(Et2dtc)with triflic acid (HOTf) afforded [Ru(Co)H(Et2dtc)(PPh3)2(OTf) (1), which has been characterized by X-ray crystallography. The RuC, RuO, average RuS and average RuP distances in 1 are 1.811(5), 2.216(3), 2.433 and 2.423 Å, respectively. Reaction of 1 with amines L results in the formation of adducts trans-[Ru(CO)(Et2dtc)(PPh3)2L](OTf) (L=N2H4 (2) and NH2OH (3)). The RuC, RuN, average RuS and average RuP distance in 3 are 1.85(1), 2.179(8), 2.433 and 2.393, respectively; the RuNO angle being 119.7(5)°. Treatment of 1 with [NnBu4][OsN(C7H6S2)2] ([C7H6S2]2−=3,4-toluenedithiolate(2−)), and [ReN(Et2dtc)2] (Et2dtc=N,N-diethyldithiocarbamate) gave the corresponding μ-nitrido complexes [Ru(CO)(Et2dtc)(PPh3)2(NOsO3)] (4), [Ru(CO)(Et2dtc)(PPh3)2{NOs(C7H6S2)2}] (5) and [Ru(CO)(Et2dtc)(PPh3)2{NRe(Et2dtc)2}] (6). The structures of complexes 4–6 have been established by X-ray crystallography. The OsN and RuN distances, and OsNRu angle in 4 are 1.719(7) and 2.075(7) Å, and 155.1(4)°, respectively. The OsN and RuN distances and OsNRu angle in 5 are 1.680(6) and 2.068(6) Å, and 166.2(3)°, respectively. The ReN and RuN distances, and ReNRu angle for 6 are 1.670(3) and 2.108(3) Å, and 170.9(2)°, respectively. The bond lengths and angles for these μ-nitrido complexes are indicative of asymmetric bridging mode of nitride, i.e. MN→Ru(II) (M=Os(VIII), Os(VI), Re(V)).
Co-reporter:Wa-Hung Leung, Willetta Lai, Ian D Williams
Journal of Organometallic Chemistry 2000 Volume 604(Issue 2) pp:197-201
Publication Date(Web):16 June 2000
DOI:10.1016/S0022-328X(00)00236-9
Interaction of [Rh(TTP)CH3] (TTP=5,10,15,20-tetra(p-tolyl)porphyrin dianion) with bidentate ligands L affords [Rh(TTP)CH3]2(μ-L) (L=4-cyanopyridine (1) or 4,4′-bipyridine (2)). The structure of 1 has been established by X-ray crystallography. The average RhC, average RhN(pyrrole), and average RhN(CNpy) distances in 1 are 2.032(4), 2.032, and 2.273(4) Å, respectively. The reaction of Na[Rh(TTP)] with (5-norbornen-2-yl)methyl iodide (C8H11I) affords [Rh(TTP)(C8H11)] (5), which has been characterized by X-ray diffraction study. The RhC and average RhN distance in 5 are 2.052(6) and 2.022 Å, respectively.
Co-reporter:Wa-Hung Leung, Eddie Y.Y. Chan, Tony C.H. Lam, Ian D. Williams
Journal of Organometallic Chemistry 2000 Volume 608(1–2) pp:139-145
Publication Date(Web):25 August 2000
DOI:10.1016/S0022-328X(00)00421-6
Treatment of [Ru(CO)2Cl2]x with NaLOEt (LOEt−=[Co(η5-C5H5){P(O)(OEt)2}3]−) afforded [LOEtRu(CO)2Cl] (1), which reacted with AgBF4 in acetone–H2O to give [LOEtRu(CO)2(H2O)][BF4] (2). Reaction of [LOEtRu(CHCHPh)(CO)(PPh3)] with HCl gave [LOEtRuCl(CO)(PPh3)] (3), which has been characterized by X-ray crystallography. The RuC, RuP, RuCl and average RuO distances in 3 are 1.993(7), 2.2811(13), 2.376(2) and 2.137 Å, respectively. Interaction of [LOEtRu(PPh3)2Cl] with CS2 and PR3 in the presence of [NH4][PF6] afforded the ruthenium(II) phosphoniodithiocarboxylate species [LOEtRu(PPh3)(η2-S2CPR3)][PF6] (R=Ph (4) or cyclohexyl (5)). Oxidation of 4 with AgBF4 yielded the ruthenium(III) complex [LOEtRu(PPh3)(η2-S2CPPh3)][BF4][PF6] (6), which has been characterized by X-ray crystallography. The RuP, average RuO and average RuS distances in 6 are 2.3978(10), 2.078 and 2.2910 Å, respectively. The ruthenium(II) thiocarbonyl complex [LOEtRu(CS)Cl(PPh3)] (7) was prepared from NaLOEt and [Ru(CS)Cl2(PPh3)2]2. The RuCl, RuP, RuC and average RuO distances in 7 are 2.3681(10), 2.3043(9), 1.823(4), and 2.140 Å, respectively. Treatment of 7 with AgBF4 in acetone–H2O afforded [LOEtRu(CS)(PPh3)(H2O)][BF4] (8). On the basis of the Ru(III/II) formal potential, CS was found to be a stronger π acid ligand than CO.
Co-reporter:Wa-Hung Leung, Man-Ching Wu, Terry K.T. Wong, Wing-Tak Wong
Inorganica Chimica Acta 2000 Volume 304(Issue 1) pp:134-136
Publication Date(Web):15 June 2000
DOI:10.1016/S0020-1693(00)00067-0
Reaction of [Cr(NBut)Cl3(dme)] (dme=1,2-dimethoxyethane) with 1,4,7-trithiacyclononane ([9]aneS3) followed by treatment with Ag(CF3SO3) leads to the isolation of [Cr(NtBu)([9]aneS3)Cl2](CF3SO3), which has been characterized by X-ray crystallography. The CrN, average CrS, and average CrCl distances are 1.640(4), 2.431, and 2.273 Å, respectively; the CrNC angle being 173.2(4)°.
Co-reporter:Wa-Hung Leung, Joyce L.C. Chim, Willetta Lai, Leo Lam, Wing-Tak Wong, Wing Hang Chan, Chi-Hung Yeung
Inorganica Chimica Acta 1999 Volume 290(Issue 1) pp:28-35
Publication Date(Web):30 June 1999
DOI:10.1016/S0020-1693(99)00096-1
Treatment of Ru(por)(NO)(OTf) (por=dianion of 2,3,7,8,12,13,17,18-octaethylporphyrin H2(OEP) or 5,10,15,20-tetra(p-tolyl)porphyrin H2(TTP), OTf=triflate) with [NnBu4][OsO3N] afforded the nitrido-bridged Ru(II)–Os(VIII) complexes [(por)(NO)RuNOsO3] (por=OEP (3) or TTP (4)). The structure of 3 has been established by X-ray crystallography. The Ru–N(O), Ru–N(Os) and Os–N distances in 3 are 1.83(2), 2.03(1) and 1.79(1) Å, respectively; the Ru–N–O and Ru–N–Os angles are 153(1) and 138.4(8)°, respectively. Reaction of Ru(por)(NO)(OTf) with [NnBu4][OsNL2] (H2L=3,4-toluenedithiol) gave the nitrido-bridged Ru(II)–Os(VI) complexes (por)(NO)RuNOsL2 (por=OEP (5), TTP (6)). Treatment of Ru(OEP)(NO)(OTf) with ReN(Et2dtc)2 (Et2dtc=N,N-diethyldithiocarbamate) afforded the Ru(II)–Re(V) complex (OEP)(NO)RuNRe(Et2dtc)2(OTf) (7). Complexes 3 and 4 exhibit porphyrin-centered oxidation along with Os(VIII)–Os(VII) and Ru(II)–Ru(I) reductions. Complexes 5 and 6 exhibit Os(VII)–Os(VI) and porphyrin ring oxidation along with Ru(II)–Ru(I) reduction.
Co-reporter:Xiao-Yi Yi, Herman H. Y. Sung, Ian D. Williams and Wa-Hung Leung
Chemical Communications 2008(Issue 28) pp:NaN3271-3271
Publication Date(Web):2008/06/11
DOI:10.1039/B800176F
Interaction of [Ce(LOEt)2(NO3)2] (LOEt− = [Co(η5-C5H5){P(O)(OEt)2}3]−) with (NH4)6[Mo7O24] in water affords the cerium(IV)-containing oxomolybdenum cluster [H4(CeLOEt)6Mo9O38], which exhibits a unique Ce6Mo9O38 core structure.
Co-reporter:Yat-Ming So, Wai-Hang Chiu, Wai-Man Cheung, Ho-Yuen Ng, Hung Kay Lee, Herman H.-Y. Sung, Ian D. Williams and Wa-Hung Leung
Dalton Transactions 2015 - vol. 44(Issue 12) pp:NaN5487-5487
Publication Date(Web):2015/02/03
DOI:10.1039/C5DT00093A
Rhenium nitrido complexes containing the Kläui tripodal ligand [Co(η5-C5H5){P(O)(OEt)2}3]− (LOEt−) have been synthesised and their reactions with [IrI(cod)Cl]2 (cod = 1,5-cyclooctadiene) and [RhII2(OAc)4] (OAc− = acetate) have been studied. The treatment of [Bun4N][ReVI(N)Cl4] with NaLOEt in methanol afforded the ReVI nitride [ReVI(LOEt)(N)Cl(OMe)] (1). Reactions of 1 with [IrI(cod)Cl]2 and [RhII2(OAc)4] gave the μ-nitrido complexes [(LOEt)(OMe)ClReVI(μ-N)IrI(cod)Cl] (2) and [RhII2(OAc)4{(μ-N)ReVI(LOEt)(OMe)Cl}2] (4), respectively. [(LOEt)Cl(PPh3)ReV(μ-N)IrI(cod)Cl] (3) and [(LOEt)Cl(PPh3)ReVI(μ-N)IrI(cod)Cl][PF6] (3·PF6) have been synthesised from the reactions of [IrI(cod)Cl]2 with [ReVLOEt(N)Cl(PPh3)] and [ReVILOEt(N)Cl(PPh3)](PF6), respectively. Similarly, the redox pair [RhII2(OAc)4{(μ-N)ReV(LOEt)(PPh3)Cl}2] (5) and [RhII2(OAc)4{(μ-N)ReVI(LOEt)(PPh3)Cl}2](PF6)2 (5·(PF6)2) have been synthesised from the reactions of [Rh2(OAc)4] with [ReVLOEt(N)Cl(PPh3)] and [ReVILOEt(N)Cl(PPh3)](PF6), respectively. While [(LOEt)Cl2RuVI(μ-N)IrI(cod)] (6) was obtained from [RuVI(LOEt)(N)Cl2] and [IrI(cod)Cl]2, the interaction between [RuVI(LOEt)(N)Cl2] and [RhII2(OAc)4] in CH2Cl2 is reversible. The crystal structures of complexes 2, 3, 3·PF6, 5, 5·(PF6)2 and 6 have been determined. X-ray crystallography indicates that the nitrido bridges in 2, 3, 3·PF6 and 6 can be described as MN—Ir (M = Re, Ru) showing Ir–N multiple bond character, whereas the interaction between ReN and Rh in 5 and 5·(PF6)2 is mostly of the donor–acceptor type. The electrochemistry of the Re nitrido complexes has been investigated by cyclic voltammetry.
Co-reporter:Ho-Yuen Ng, Wai-Man Cheung, Enrique Kwan Huang, Kang-Long Wong, Herman H.-Y. Sung, Ian D. Williams and Wa-Hung Leung
Dalton Transactions 2015 - vol. 44(Issue 42) pp:NaN18468-18468
Publication Date(Web):2015/09/24
DOI:10.1039/C5DT02513C
Ruthenium thio- and seleno-nitrosyl complexes containing chelating sulfur and oxygen ligands have been synthesised and their de-chalcogenation reactions have been studied. The reaction of mer-[Ru(N)Cl3(AsPh3)2] with elemental sulfur and selenium in tetrahydrofuran at reflux afforded the chalcogenonitrosyl complexes mer-[Ru(NX)Cl3(AsPh3)2] [X = S (1), Se (2)]. Treatment of 1 with KN(R2PS)2 afforded trans-[Ru(NS)Cl{N(R2PS)2}2] [R = Ph (3), Pri (4), But (5)]. Alternatively, the thionitrosyl complex 5 was obtained from [Bun4N][Ru(N)Cl4] and KN(But2PS)2, presumably via sulfur atom transfer from [N(But2PS)2]− to the nitride. Reactions of 1 and 2 with NaLOEt (LOEt− = [Co(η5-C5H5){P(O)(LOEt)2}3]−) gave [Ru(NX)LOEtCl2] (X = S (8), Se (9)). Treatment of [Bun4N][Ru(N)Cl4] with KN(R2PS)2 produced RuIV–RuIV μ-nitrido complexes [Ru2(μ-N){N(R2PS)2}4Cl] [R = Ph (6), Pri (7)]. Reactions of 3 and 9 with PPh3 afforded 6 and [Ru(NPPh3)LOEtCl2], respectively. The desulfurisation of 5 with [Ni(cod)2] (cod = 1,5-cyclooctadiene) gave the mixed valance RuIII–RuIV μ-nitrido complex [Ru2(μ-N){N(But2PS)2}4] (10) that was oxidised by [Cp2Fe](PF6) to give the RuIV–RuIV complex [Ru2(μ-N){N(But2PS)2}4](PF6) ([10]PF6). The crystal structures of 1, 2, 3, 7, 9 and 10 have been determined.
Co-reporter:Ho-Fai Ip, Xiao-Yi Yi, Wai-Yeung Wong, Ian D. Williams and Wa-Hung Leung
Dalton Transactions 2011 - vol. 40(Issue 41) pp:NaN11050-11050
Publication Date(Web):2011/09/19
DOI:10.1039/C1DT10306G
Ruthenium nitrosyl complexes containing the Kläui's oxgyen tripodal ligand LOEt− ([CpCo{P(O)(OEt)2}3]− where Cp = η5-C5H5) were synthesized and their photolysis studied. The treatment of [Ru(N⁁N)(NO)Cl3] with [AgLOEt] and Ag(OTf) afforded [LOEtRu(N⁁N)(NO)][OTf]2 where N⁁N = 4,4′-di-tert-butyl-2,2′-bipyridyl (dtbpy) (2·[OTf]2), 2,2′-bipyridyl (bpy) (3·[OTf]2), N,N,N′N′-tetramethylethylenediamine (4·[OTf]2). Anion metathesis of 3·[OTf]2 with HPF6 and HBF4 gave 3·[PF6]2 and 3·[BF4]2, respectively. Similarly, the PF6− salt 4·[PF6]2 was prepared by the reaction of 4·[OTf]2 with HPF6. The irradiation of [LOEtRu(NO)Cl2] (1) with UV light in CH2Cl2-MeCN and tetrahydrofuran (thf)-H2O afforded [LOEtRuCl2(MeCN)] (5) and the chloro-bridged dimer [LOEtRuCl]2(μ-Cl)2 (6), respectively. The photolysis of complex [2][OTf]2 in MeCN gave [LOEtRu(dtbpy)(MeCN)][OTf]2 (7). Refluxing complex 5 with RNH2 in thf gave [LOEtRuCl2(NH2R)] (R = tBu (8), p-tol (9), Ph (10)). The oxidation of complex 6 with PhICl2 gave [LOEtRuCl3] (11), whereas the reduction of complex 6 with Zn and NH4PF6 in MeCN yielded [LOEtRu(MeCN)3][PF6] (12). The reaction of 3·[BF4]2 with benzylamine afforded the μ-dinitrogen complex [{LOEtRu(bpy)}2(μ-N2)][BF4]2 (13) that was oxidized by [Cp2Fe]PF6 to a mixed valence RuII,III species. The formal potentials of the RuLOEt complexes have been determined by cyclic voltammetry. The structures of complexes 5,6,10,11 and 13 have been established by X-ray crystallography.
Co-reporter:Ka-Chun Au-Yeung, Yat-Ming So, Guo-Cang Wang, Herman H.-Y. Sung, Ian D. Williams and Wa-Hung Leung
Dalton Transactions 2016 - vol. 45(Issue 13) pp:NaN5438-5438
Publication Date(Web):2016/03/02
DOI:10.1039/C6DT00267F
Reactions of [CeIV(LOEt)2Cl2] (LOEt− = [Co(η5-C5H5){P(O)(OEt)2}3]−) and [CeIV2(μ-O){N(Pri2PO)2}4Cl2] with PhIO afford the λ3-iodane complexes [CeIV(LOEt)2{OI(Cl)Ph}2] and [CeIV2{N(Pri2PO)2}3{OI(Cl)Ph}], respectively, whereas that between [CeIV(LOEt)2Cl2] and PhIO2 or excess PhIO yields the λ5-iodane adduct [CeIV(LOEt)2{OI(O)ClPh}2]. The crystal structures of the CeIV λ3- and λ5-iodane complexes have been determined and their oxo transfer reactivities have been investigated.
Co-reporter:Kang-Long Wong, Yat-Ming So, Guo-Cang Wang, Herman H.-Y. Sung, Ian D. Williams and Wa-Hung Leung
Dalton Transactions 2016 - vol. 45(Issue 21) pp:NaN8776-8776
Publication Date(Web):2016/04/26
DOI:10.1039/C6DT00678G
Heterometallic CeIV/M (M = MoVI, ReVII, VV) oxo clusters supported by the Kläui tripodal oxygen ligand [(η5-C5H5)Co{P(O)(OEt)2}3]− (LOEt−) have been synthesized and structurally characterized, and the catalytic activity of the CeIV/VV oxo cluster in the oxidation of thioanisoles has been studied. Treatment of [Ce(LOEt)Cl3] (1) with [Ag2MoO4] afforded the reported CeIV/MoVI cluster [H4(CeLOEt)6Mo9O38] (2), whereas that with [AgReO4] yielded the CeIV/ReVII cluster [{LOEtCe(ReO4)2(H2O)(μ-ReO4)}2] (3) that contains an 8-membered Ce2Re2O4 ring. Treatment of 1 with [Ag3VO4] afforded the CeIV/VV cluster [H2(CeLOEt)4(VO)4(μ4-O)(μ3-O)12] (4) containing a {Ce4V4O13} oxo-metallic core. The solid-state structure of 4 consists of four {VO4}3− units bridged by four {LOEtCe3+} moieties and a μ4-oxo ligand. Each Ce atom in 4 is 9-coordinated, whereas the geometry around each V atom is pseudo square pyramidal with a terminal oxo at the apical position. Cluster 4 is an active catalyst for the oxidation of substituted thioanisoles with tert-butyl hydroperoxide. For example, the oxidation of thioanisole with tert-butyl hydroperoxide in the presence of 0.01 mol% of 4 gave a ca. 30:1 mixture of the sulfoxide and sulfone products in 96% yield.
![1,2-Ethanediamine, N,N'-bis[[2-(methylsulfinyl)phenyl]methylene]-](http://img.cochemist.com/ccimg/611200/611183-26-7.png)
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![BENZENE, 1-(DIETHOXYMETHYL)-2-[(4-METHYLPHENYL)SULFINYL]-](http://img.cochemist.com/ccimg/611200/611183-10-9_b.png)
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![Oxirane, 2-ethyl-3-[2-(phenylmethoxy)ethyl]-, cis-](http://img.cochemist.com/ccimg/138700/138624-28-9_b.png)
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-](http://img.cochemist.com/ccimg/12100/12086-08-7.png)
-](http://img.cochemist.com/ccimg/12100/12086-08-7_b.png)
![bis[(2,3,5,6-η)-bicyclo[2.2.1]hepta-2,5-diene]di-μ-chlorodirhodium](http://img.cochemist.com/ccimg/12300/12257-42-0.png)
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