Co-reporter:Fangjun Zhang, Jie ZhangXigeng Zhou
Inorganic Chemistry 2017 Volume 56(Issue 4) pp:
Publication Date(Web):February 6, 2017
DOI:10.1021/acs.inorgchem.6b02747
Treatment of the yttrium dialkyl complex TpMe2Y(CH2Ph)2(THF) (TpMe2 = tri(3,5 dimethylpyrazolyl)borate, THF = tetrahydrofuran) with S8 in a 1:1 molar ratio in THF at room temperature afforded a yttrium pentasulfide TpMe2Y(κ4-S5) (THF) (1) in 93% yield. The yttrium monoalkyl complex TpMe2CpYCH2Ph(THF) reacted with S8 in a 1:0.5 molar ratio under the same conditions to give another yttrium pentasulfide [(TpMe2)2Y]+[Cp2Y(κ4-S5)]− (10) in low yield. Further investigations indicated that the S52– anion facilely turned into the corresponding thioethers or organic disulfides, and released the redundant S8, when it reacted with some electrophilic reagents. The mechanism for the formation of the S52– ligand has been investigated by the controlling of the reaction stoichiometric ratios and the stepwise reactions.
Co-reporter:Dr. Weiyin Yi;Dr. Jie Zhang;Shujian Huang;Dr. Linhong Weng ;Dr. Xigeng Zhou
Chemistry - A European Journal 2014 Volume 20( Issue 3) pp:867-876
Publication Date(Web):
DOI:10.1002/chem.201303608
Abstract
Unusual chemical transformations such as three-component combination and ring-opening of N-heterocycles or formation of a carbon–carbon double bond through multiple C–H activation were observed in the reactions of TpMe2-supported yttrium alkyl complexes with aromatic N-heterocycles. The scorpionate-anchored yttrium dialkyl complex [TpMe2Y(CH2Ph)2(THF)] reacted with 1-methylimidazole in 1:2 molar ratio to give a rare hexanuclear 24-membered rare-earth metallomacrocyclic compound [TpMe2Y(μ-N,C-Im)(η2-N,C-Im)]6 (1; Im=1-methylimidazolyl) through two kinds of C–H activations at the C2- and C5-positions of the imidazole ring. However, [TpMe2Y(CH2Ph)2(THF)] reacted with two equivalents of 1-methylbenzimidazole to afford a C–C coupling/ring-opening/C–C coupling product [TpMe2Y{η3-(N,N,N)-N(CH3)C6H4NHCHC(Ph)CN(CH3)C6H4NH}] (2). Further investigations indicated that [TpMe2Y(CH2Ph)2(THF)] reacted with benzothiazole in 1:1 or 1:2 molar ratio to produce a C–C coupling/ring-opening product {(TpMe2)Y[μ-η2:η1-SC6H4N(CHCHPh)](THF)}2 (3). Moreover, the mixed TpMe2/Cp yttrium monoalkyl complex [(TpMe2)CpYCH2Ph(THF)] reacted with two equivalents of 1-methylimidazole in THF at room temperature to afford a trinuclear yttrium complex [TpMe2CpY(μ-N,C-Im)]3 (5), whereas when the above reaction was carried out at 55 °C for two days, two structurally characterized metal complexes [TpMe2Y(Im-TpMe2)] (7; Im-TpMe2=1-methyl-imidazolyl-TpMe2) and [Cp3Y(HIm)] (8; HIm=1-methylimidazole) were obtained in 26 and 17 % isolated yields, respectively, accompanied by some unidentified materials. The formation of 7 reveals an uncommon example of construction of a CC bond through multiple C–H activations.
Co-reporter:Yin Zhang, Jie Zhang, Jianquan Hong, Fangjun Zhang, Linhong Weng, and Xigeng Zhou
Organometallics 2014 Volume 33(Issue 24) pp:7052-7058
Publication Date(Web):December 2, 2014
DOI:10.1021/om500500b
The reactions of β-diketiminatoyttrium dialkyl complex LY(CH2Ph)2(THF) (1, L = [{N(2,6-iPr2C6H3)C(Me)}2CH]−) with a series of aromatic N-heterocycles such as 2-phenylpyridine, benzothiazole, and benzoxazole were studied and displayed discrete reactivity including C–H activation, C–C coupling, ring-opening/insertion, and dearomatization. The reaction of 1 with 2-phenylpyridine in 1:2 molar ratio in THF at 30 °C for 14 days afforded a structurally characterized metal complex, LY(η2-N,C-C5H4NC6H4-2)[C5H4N(CH2Ph-4)Ph] (2), in 73% isolated yield, indicating the occurrence of phenyl ring C(sp2)–H activation and pyridine ring 1,4-addition/dearomatization. However, when this reaction was done at 5 °C for 7 days, it gave the pyridine ring 1,2-addition product LY(η2-N,C-C5H4NC6H4-2)[C5H4N(CH2Ph-2)Ph] (3) in 54% isolated yield. Further investigations revealed that complex 2 is the thermodynamic controlled product and complex 3 is the kinetically controlled product; 3 converted slowly into 2, as confirmed by 1H NMR spectroscopy. The equimolar reaction of 1 with benzothiazole or benzoxazole produced two C–C coupling/ring-opening/insertion products, LY[η2-S,N-SC6H4NCH(CH2Ph)2](THF) (4) and {LY[μ-η2:η1-O,N-OC6H4NCH(CH2Ph)2]}2 (5), in 84% and 78% isolated yields, respectively.
Co-reporter:Fangjun Zhang, Jie Zhang, Yin Zhang, Jianquan Hong, and Xigeng Zhou
Organometallics 2014 Volume 33(Issue 21) pp:6186-6192
Publication Date(Web):October 13, 2014
DOI:10.1021/om5008665
A high-efficiency and atom-economic route for the synthesis of N-aryl-substituted propiolamidines was established through the addition of terminal alkynes with aryl-substituted symmetrical or unsymmetrical carbodiimides catalyzed by mixed TpMe2/Cp rare-earth-metal alkyl complexes (TpMe2)CpLnCH2Ph(THF) (1Ln). Moreover, the gadolinium alkyl complex 1Gd can also serve as a catalyst for the double addition of dialkynes with carbodiimides. Mechanism studies indicated that the variable coordination modes (κ3 or κ2) of the TpMe2 ligand on the rare-earth-metal species may play an important role in the catalytic cycles.
Co-reporter:Jie Zhang, Weiyin Yi, Zhenxia Chen and Xigeng Zhou
Dalton Transactions 2013 vol. 42(Issue 16) pp:5826-5831
Publication Date(Web):11 Feb 2013
DOI:10.1039/C3DT00014A
The dissociation of the anionic guanidinate ligand NC(NMe2)2 promoted by rare-earth metal complexes at room temperature is described. Treatment of CpLnCl2(THF)3 with two equiv. of Li[NC(NMe2)2] in THF at room temperature affords [Cp2Ln(μ-η1:η2-L2)]2 (Ln = Y; L = NC(NMe2)NC(NMe2)2) and CpLn[NC(NMe2)2](μ-η1:η2-L)2LnCp2 (Ln = Dy) in moderated yields, respectively. YCl3 reacts with three equiv. of Li[NC(NMe2)2] under the same conditions to give a trinuclear yttrium guanidinate [(Me2N)2CN]5Y3[μ-NC(NMe2)2]2(μ-η1:η2-L)2 in 63% yield. These reactions show that rare-earth metals can promote a C–N bond cleavage of the guanidine anion [NC(NMe2)2]− at room temperature. All new complexes were characterized by elemental analysis and spectroscopic properties, and their solid-state structures were determined through single-crystal X-ray diffraction analysis.
Co-reporter:Weiyin Yi ; Shujian Huang ; Jie Zhang ; Zhenxia Chen ;Xigeng Zhou
Organometallics 2013 Volume 32(Issue 19) pp:5409-5415
Publication Date(Web):September 12, 2013
DOI:10.1021/om400698j
The TpMe2-supported yttrium dialkyl TpMe2Y(CH2Ph)2(THF) (TpMe2 = tri(3,5-dimethylpyrazolyl)borate) reacted with 1 equiv of ArNH2 in THF at room temperature to afford the yttrium alkyl primary amido complexes TpMe2YNHAr(CH2Ph)(THF) (Ar = Ph (1), C6H3-iPr2-2,6 (2)) in 84% and 88% isolated yields, respectively. Complex 1 reacted with iPrN═C═NiPr in THF at room temperature to give a yttrium dianionic guanidinate complex, TpMe2Y[(iPrN)2C═NPh](THF)2 (3, 74%). However, the reaction of 1 with ArN═C═NAr (Ar = C6H3-iPr2-2,6) in the same conditions produced a Y–C bond insertion product, TpMe2Y[(ArN)2CCH2Ph](NHPh) (4, 87%). Moreover, treatment of 2 with 1 equiv of iPrN═C═NiPr in THF at room temperature afforded two yttrium complex, TpMe2Y[(iPrN)C═NAr](THF) (5) and TpMe2Y[(iPrN)2CCH2Ph](NHAr) (6), in 58% and 19% isolated yields, respectively. These results indicated that carbodiimide can selectively insert into the Y–CH2Ph and Y–NHAr σ-bonds of TpMe2-supported yttrium alkyl primary amido complexes TpMe2YNHAr(CH2Ph)(THF), and this selectivity depends on the steric hindrance of the substituent groups R of cabodiimides and the primary amido ligands. All these new complexes were characterized by elemental analysis and spectroscopic methods, and their solid-state structures except 1 were also confirmed by single-crystal X-ray diffraction analysis.
Co-reporter:Dr. Weiyin Yi;Dr. Fangjun Zhang;Yin Zhang;Dr. Zhenxia Chen;Dr. Xigeng Zhou
Chemistry - A European Journal 2013 Volume 19( Issue 36) pp:11975-11983
Publication Date(Web):
DOI:10.1002/chem.201300610
Abstract
A series of unusual chemical-bond transformations were observed in the reactions of high active yttriumdialkyl complexes with unsaturated small molecules. The reaction of scorpionate-anchored yttriumdibenzyl complex [TpMe2Y(CH2Ph)2(thf)] (1, TpMe2=tri(3,5-dimethylpyrazolyl)borate) with phenyl isothiocyanate led to CS bond cleavage to give a cubane-type yttrium–sulfur cluster, {TpMe2Y(μ3-S)}4 (2), accompanied by the elimination of PhNC(CH2Ph)2. However, compound 1 reacted with phenyl isocyanate to afford a C(sp3)H activation product, [TpMe2Y(thf){μ-η1:η3-OC(CHPh)NPh}{μ-η3:η2-OC(CHPh)NPh}YTpMe2] (3). Moreover, compound 1 reacted with phenylacetonitrile at room temperature to produce γ-deprotonation product [(TpMe2)2Y]+[TpMe2Y(N=CCHPh)3]− (6), in which the newly formed NCCHPh ligands bound to the metal through the terminal nitrogen atoms. When this reaction was carried out in toluene at 120 °C, it gave a tandem γ-deprotonation/insertion/partial-TpMe2-degradation product, [(TpMe2Y)2(μ-Pz)2{μ-η1:η3-NC(CH2Ph)CHPh}] (7, Pz=3,5-dimethylpyrazolyl).
Co-reporter:Weiyin Yi, Jie Zhang, Zhenxia Chen, and Xigeng Zhou
Inorganic Chemistry 2012 Volume 51(Issue 20) pp:10631-10638
Publication Date(Web):September 24, 2012
DOI:10.1021/ic3008552
A novel TpMe2-supported (TpMe2 = tri(3,5-dimethylpyrazolyl)borate) rare earth metal complex promoted Me–Si cleavage of the bis(trimethylsilyl) amide ligand ([(Me3Si)2N]−) was observed. Reaction of TpMe2LnCl2 with 2 equiv of K[(RN)2CN(SiMe3)2] (KGua) gave the methylamidinate complexes TpMe2Ln[(RN)2CMe][N(SiMe3)2] (R = isopropyl, Ln = Y (1Y), Er (1Er); R = cyclohexyl, Ln = Y (2Y)) in moderate yields. In contrast, TpMe2YCl2(THF) reacted with 1 equiv of KGua to afford a C–N cleavage product TpMe2Y(Cl)N(SiMe3)2(THF) (4), indicating that this guanidinate ligand is not stable in the yttrium complex with the TpMe2 ligand, and a carbodiimide deinsertion takes place easily. The mechanism for the formation of complexes 1 and 2 was also studied by controlling the substrate stoichiometry and the reaction sequence and revealed that the bis(trimethylsilyl)amine anion N(SiMe3)2– can undergo two routes of γ-methyl deprotonation and Si–Me cleavage for its functionalizations. All these new complexes were characterized by elemental analysis and spectroscopic methods, and their solid-state structures were also confirmed by single-crystal X-ray diffraction.
Co-reporter:Jie Zhang, Zhengxing Zhang, Zhenxia Chen and Xigeng Zhou
Dalton Transactions 2012 vol. 41(Issue 2) pp:357-359
Publication Date(Web):14 Nov 2011
DOI:10.1039/C1DT11383F
Two novel eight-nuclear lanthanide oxide and chloride clusters Ln8(μ-η2-L4)2(μ3-Cl)4(μ-Cl)10(μ4-O)3(THF)8 (Ln = Er(3), Dy(4); L4 = [OC{(Me)CN-2,6-iPrC6H3}2]2−) have been synthesized by the reaction of β-diketiminate rare-earth metal chlorides with oxygen, providing a new oxidation and coupling reaction of the β-diketiminate ligand.
Co-reporter:Weiyin Yi, Jie Zhang, Zhenxia Chen, and Xigeng Zhou
Organometallics 2012 Volume 31(Issue 20) pp:7213-7221
Publication Date(Web):October 2, 2012
DOI:10.1021/om3007773
The mixed TpMe2/Cp-supported yttrium monoalkyl (TpMe2)CpYCH2Ph(THF) (1) reacted with 1 equiv of PhCN in THF at room temperature to afford the imine–enamine tautomer (TpMe2)CpY(N(H)C(Ph)═CHPh)(THF) (2) and the insertion product (TpMe2)CpY(N═C(CH2Ph)Ph)(THF) (3), in 61% and 12% isolated yields, respectively. 2 further reacted with PhCN in toluene at 120 °C to give the N–H bond addition product (TpMe2)CpY(N(H)C(Ph)NC(Ph)═CHPh) (4). Treatment of 1 with 1 equiv of anthranilonitrile produced the dimer [(TpMe2)CpY(μ-NHC6H4CN)]2 (5). The monomer product (TpMe2)CpY(NHC6H4CN)(HMPA) (6) can be obtained through the coordination of HMPA (hexamethylphosphoric triamide). The reaction of 5 with 1 in THF at room temperature gave the cyano group insertion product [(TpMe2)CpY(THF)]2(μ-NHC6H4C(CH2Ph)═N) (7). However, this reaction under the heating conditions gave an unexpected rearrangement product, (TpMe2)CpY(THF)(η2-NHC6H4C(CH2Ph)═NH) (8). 5 further reacted with o-aminobenzonitrile at 120 °C to afford the nucleophilic addition/cyclization product TpMe2Y[κ3-(4-NH═(C8N2H4)(2-NHC6H4)](HMPA) (9), accompanied with the elimination of the Cp ring. These results indicated that the yttrium alkyl complex exhibits high activity toward organic nitriles and reveals some unusual transformations during the insertion process. All these new complexes were characterized by elemental analysis and spectroscopic methods, and their solid-state structures were also confirmed by single-crystal X-ray diffraction analysis.
Co-reporter:Weiyin Yi ; Jie Zhang ; Meng Li ; Zhenxia Chen ;Xigeng Zhou
Inorganic Chemistry 2011 Volume 50(Issue 22) pp:11813-11824
Publication Date(Web):October 27, 2011
DOI:10.1021/ic2019499
The structurally characterized TpMe2-supported rare earth metal monoalkyl complex (TpMe2)CpYCH2Ph(THF) (1) was synthesized via the salt-metathesis reaction of (TpMe2)CpYCl(THF) with KCH2Ph in THF at room temperature. Treatment of 1 with 1 equiv of PhC≡CH under the same conditions afforded the corresponding alkynyl complex (TpMe2)CpYC≡CPh(THF) (2). Complex 1 exhibits high activity toward carbodiimides, isocyanate, isothiocyanate, and CS2; treatment of 1 with such substrates led to the formation of a series of the corresponding Y–C(benzyl) σ-bond insertion products (TpMe2)CpY[(RN)2CCH2Ph] (R = iPr(3a), Cy(3b), 2,6-iPr–C6H3(3c)), (TpMe2)CpY[SC(CH2Ph)NPh] (4), (TpMe2)CpY[OC(CH2Ph)NPh] (5), and (TpMe2)CpY(S2CCH2Ph) (6) in 40–70% isolated yields. Carbodiimides and isothiocyanate can also insert into the Y–C(alkynyl) σ bond of 2 to yield complexes (TpMe2)CpY[(RN)2CC≡CPh] (R = iPr(7a), Cy(7b)) and (TpMe2)CpY[SC(C≡CPh)NPh] (9). Further investigation results indicated that 1 can effectively catalyze the cross-coupling reactions of phenylacetylene with carbodiimides. However, treatment of o-allylaniline with a catalytic amount of 1 gave only the benzyl abstraction product (TpMe2)CpY(NHC6H4CH2CH═CH2-o)(THF) (10), without observation of the expected organic hydroamination/cyclization product. All of these new complexes were characterized by elemental analysis and spectroscopic properties, and their solid-state structures were also confirmed by single-crystal X-ray diffraction analysis.
Co-reporter:Jie Zhang, Yanan Han, Zhenxia Chen and Xigeng Zhou
Dalton Transactions 2011 vol. 40(Issue 36) pp:9098-9100
Publication Date(Web):15 Aug 2011
DOI:10.1039/C1DT10990A
Reaction of two equiv of [2-NCC6H4HNLi(THF)]n (1) with Cp2LnCl(THF) yields the heterobimetallic complexes Cp2Ln[κ3-(4-NH(C8N2H4)(2-NHC6H4)]Li(THF)3 (Cp = C5H5; Ln = Er (2), Y(3)), indicating an organolanthanide-mediated nucleophilic addition/cyclization of the 2-cyanobenzoamino anion to construct the 4-iminoquinazolinate dianionic ligand.
Co-reporter:Weiyin Yi, Jie Zhang, Longcheng Hong, Zhenxia Chen, and Xigeng Zhou
Organometallics 2011 Volume 30(Issue 21) pp:5809-5814
Publication Date(Web):October 10, 2011
DOI:10.1021/om2006722
The synthesis, structure, and reactivity of organoyttrium phosphides toward phenyl isocyanate (PhNCO) and phenyl isothiocyanate (PhNCS) are described. Reaction of (TpMe2)CpYCH2Ph(THF) (TpMe2 = tris(3,5-dimethylpyrazolyl)borate; Cp = C5H5) with 1 equiv of HPPh2 in THF at ambient temperature gives an organoyttrium phosphide (TpMe2)CpYPPh2(THF) (1). Treatment of 1 with 1 equiv of PhNCO in THF at ambient temperature results in monoinsertion of PhNCO into the Y–P σ-bond to yield complex (TpMe2)CpY[OC(PPh2)NPh](THF) (2), whereas reaction of 1 with 2 equiv of PhNCO affords the PhNCO diinsertion product (TpMe2)CpY[OC(PPh2)N(Ph)C(O)NPh] (4). However, reaction of 1 with PhNCS under the same conditions is independent of the stoichiometric ratio and gives only the monoinsertion product (TpMe2)CpY[SC(PPh2)NPh] (3). Moreover, 1 can effectively catalyze the cyclotrimerization of PhNCO under mild conditions, but does not catalyze the cyclotrimerization of PhNCS. In addition, the reaction of Cp2LnPPh2(THF) with PhNCS affords the insertion products Cp2Ln[SC(PPh2)NPh](THF) (Ln = Y (6), Er (7), Dy (8)). All new complexes were characterized by elemental analysis, IR, and/or 1H, 13C and 31P NMR, and their solid-state structures, except 4, were determined through single-crystal X-ray diffraction analysis. These reactions represent the first example of isocyanate and isothiocyanate insertions into the Ln–P σ-bond and provide an efficient method for the construction of phosphaureido, phosphadiureido, and phosphathioureido ligands.
Co-reporter:Jie Zhang, Weiyin Yi, Zhengxing Zhang, Zhenxia Chen, and Xigeng Zhou
Organometallics 2011 Volume 30(Issue 16) pp:4320-4324
Publication Date(Web):July 26, 2011
DOI:10.1021/om2003877
A “new” strategy for the preparation of organolanthanide neutral hydrides by the reaction of organolanthanide chlorides with metallic potassium and their reactivity toward isocyanide has been studied. Treatment of [Me2Si(C5H4)2LnCl]2 with excess metallic potassium in THF results in a direct chlorine-abstracted reaction to yield the corresponding organolanthanide hydrides {μ-[η5-Me2Si(C5H4)2Ln]}2(μ-H)2 (Ln = Y (1), Er (2), Gd (3)) in moderate yields. Structural determination results indicated that complex 1 is a solvated neutral dimer with two bridging hydrogen atoms. Further investigations on their reactivity display that tert-butyl isocyanide (CNtBu) readily inserts into the Ln–H bonds of 1–3 to form lanthanocene N-alkylformimidoyl complexes {μ-[η5-Me2Si(C5H4)2Ln]}2(μ,η2-HC═NCMe3)2 (Ln = Y (4), Er (5), Gd (6)). All compounds were characterized by elemental analysis and spectroscopic properties. The solid-state structures of complexes 1 and 4–6 were determined through X-ray single-crystal diffraction analysis.
Co-reporter:Fuyan Han ; Jie Zhang ; Weiyin Yi ; Zhengxing Zhang ; Jingyi Yu ; Linhong Weng ;Xigeng Zhou
Inorganic Chemistry 2010 Volume 49(Issue 6) pp:2793-2798
Publication Date(Web):February 9, 2010
DOI:10.1021/ic902296d
TpMe2LnCl2 (1) reacts with 2 equiv of KN(SiMe3)2 in tetrahydrofuran at room temperature to yield the ligand redistribution/γ-deprotonation products [(TpMe2)2Ln]+[((Me3Si)2N)2Ln(CH2)SiMe2N(SiMe3)]− [Ln = Er (2), Y (3)]. Complex 2 can also be obtained by reacting [(Me3Si)2N]2ErCl with KTpMe2. However, 1 reacts with 1.5 and 1 equiv of KN(SiMe3)2 to yield [(TpMe2)2Er]+[((Me3Si)2N)3ErCl]− (4) and [(TpMe2)2Er]+{[(Me3Si)2N)TpMe2ErCl]2(μ-Cl)2K}− (5), respectively. Furthermore, it is found that 2 reacts with 2 equiv of CyN═C═NCy (Cy = cyclohexyl) to give the tandem HN(SiMe3)2 elimination and Ln−C insertion product (TpMe2)Er[(CyN)2CCH2SiMe2N(SiMe3)] (6) in 71% isolated yield. The results reveal that the γ-deprotonation degree of advancement increases with an increase of the steric hindrance around the central metal ion. All new complexes have been characterized by elemental analysis and spectroscopic properties, and their solid-state structures have also been determined through single-crystal X-ray diffraction analysis.
Co-reporter:Jie Zhang, Fuyan Han, Yanan Han, Zhenxia Chen and Xigeng Zhou
Dalton Transactions 2009 (Issue 10) pp:1806-1811
Publication Date(Web):26 Jan 2009
DOI:10.1039/B817776G
A salt elimination reaction of bis(cyclopentadienyl)titanium dichloride (C5H5)2TiCl2 with one equiv. of N,N′-tetramethylguanidinate lithium [LiNC(NMe2)2] proceeded in THF at room temperature to yield a bis(cyclopentadienyl)titanium mono-guanidinate chloride (C5H5)2TiCl(NC(NMe2)2) (1). However, treatment of two equiv. of LiNC(NMe2)2 with (C5H5)2TiCl2 under the same conditions resulted in the elimination of one cyclopentadienyl ring to form an unexpected mono(cyclopentadienyl)titanium bis(guanidinate) chloride (C5H5)TiCl[NC(NMe2)2]2 (2), in which only one Ti–Cl bond is broken, with the other Ti–Cl bond retained. Reaction of [(C5H5)2YCl]2 with LiNC(NMe2)2 gave the corresponding product {(C5H5)2Y[μ-η1:η2-NC(NMe2)2]}2 (3). On further investigations on the reactivity of 1–3 toward phenyl isocyanate, we found phenyl isocyanate only inserts into the Y–N(μ-Gua) bonds of 3 to yield [(C5H5)2Y(μ-η1:η2-OC(NC(NMe2)2)NPh)]2 (4). Complexes 1–4 were characterized by elemental analysis and spectroscopic properties and their solid-state structures were determined by X-ray single-crystal diffraction.
Co-reporter:Jie Zhang, Liping Ma, Yanan Han, Fuyan Han Zhengxing Zhang, Ruifang Cai, Zhenxia Chen and Xigeng Zhou
Dalton Transactions 2009 (Issue 17) pp:3298-3305
Publication Date(Web):04 Feb 2009
DOI:10.1039/B813711K
The reaction of N,N′-dicyclohexylcarbodiimide (DCCI) with [Cp2Yb(o-H2NC6H4S)]2 (Cp = C5H5) (1) forms the monomer product Cp2Yb[SC6H4NC(NHCy)2] (2), indicating that the adjacent NH2group can add to the CN double bonds of carbodiimide to construct a neutral guanidine group. When DCCI reacts with [Cp2Y(o-H2NC6H4S)]2·2THF (4), a dimer product [CpY(μ-η2:η1-SC6H4NC(NHCy)NCy)(THF)]2 (5) was isolated, through the amino group addition and cyclopentadienyl elimination. Interestingly, on treatment of 4 with one or two equivalent of iPrNCNiPr at the same conditions gave an amino group partial addition product CpY(THF)[μ-η2:η1-SC6H4NC(NHiPr)NiPr)](μ-η2:η1-SC6H4NH2)YCp2·THF (6), where only one NH2group can add to the CN double bonds of carbodiimide molecule, another one is remained. However, when we extended this reaction to the gadolinium complex, a novel co-crystalline compound {Cp2Gd[SC6H4NC(NHCy)2]}·{CpGd(THF)[μ-η2:η1-SC6H4NC(NHCy)NCy)][μ-η2:η1-SC6H4NH2]GdCp2·THF} (8) was obtained from the reaction of [Cp2Gd(o-H2NC6H4S)]2 (7) with DCCI. In order to investigate the sequence of addition and the elimination of the cyclopentadienyl group, a deprotonation reaction of the addition product has also been studied. Reaction of CpYb[SC6H4NC(NHiPr)2]2(THF) (9), formed by reaction of Cp3Yb with two equivalent of o-aminothiophenol, and subsequently with 2 equiv. of iPrNCNiPr, with one equiv. of Cp3Yb gave a cyclopentadienyl elimination product [CpYb(μ-η2:η1-SC6H4NC(NHiPr)NiPr)(THF)]2 (3). This result reveals that addition of the NH2group to carbodiimide is prior to the elimination of cyclopentadienyl group. All of new compounds have been characterized by elemental analysis and spectroscopic properties. The solid-state structures of complexes 2, and 5–9 were determined by single-crystal X-ray diffraction.
Co-reporter:Jie Zhang ; Yanan Han ; Fuyan Han ; Zhenxia Chen ; Linhong Weng ;Xigeng Zhou
Inorganic Chemistry 2008 Volume 47(Issue 13) pp:5552-5554
Publication Date(Web):June 13, 2008
DOI:10.1021/ic800782r
Compounds Cp2Ln[κ3-(4-NH(C8N2H4)(2-NH2C6H4)] [Cp = C5H5; Ln = Er (1), Y (2)] were synthesized by the reaction of Cp2LnNiPr2(THF) with anthranilonitrile, indicating a novel organolanthanide-mediated intermolecular nucleophilic addition/cyclization of anthranilonitrile. To trap the intermediate I, a probe reaction of Cp2ErNiPr2(THF) with anthranilonitrile and carbodiimide has also been investigated.
Co-reporter:Jie Zhang;Ruifang Cai;Minqing Chen;Linhong Weng;Xigeng Zhou
European Journal of Inorganic Chemistry 2005 Volume 2005(Issue 16) pp:
Publication Date(Web):14 JUL 2005
DOI:10.1002/ejic.200500229
The reaction of YbI2(THF)2 with TPPLi2 (TPP = 5,10,15,20-tetraphenylporphyrin) in THF, and then with 0.5 equiv. of C60, which was solvated in toluene beforehand, gave the title compound {[TPPYb(μ-OH)2Yb(THF)TPP]·C60}n, which is the first example of a rare earth metallofullerene cocrystal compound. X-ray structural analyses indicate that this compound displays a complicated supramolecular structure, which contains some unique noncovalent interactionsbetween C60 and the rare earth metalloporphyrin units. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2005)
Co-reporter:Liping Ma, Jie Zhang, Ruifang Cai, Zhenxia Chen, Linhong Weng, Xigeng Zhou
Journal of Organometallic Chemistry 2005 Volume 690(21–22) pp:4926-4932
Publication Date(Web):1 November 2005
DOI:10.1016/j.jorganchem.2005.08.005
The synthesis and reactivity of new lanthanocene complexes incorporating phenothiazine ligand are described. The reaction of phenothiazine (HPtz) with nBuLi in THF and subsequently with 1 equiv. of (C5H5)2LnCl(THF) gave the original complexes (C5H5)2LnPtz(THF) (Ln = Yb(1), Er(2), Dy(3), Y(4)). Treatment of complexes 1–4 with N,N′-diisopropylcarbodiimide results in mono-insertion of carbodiimide into the Ln–N(Ptz)-bond to yield the corresponding guanidinates (C5H5)2Ln[(iPrN)2C(Ptz)] (Ln = Yb (5), Er (6), Dy (7), Y(8)). Further investigations indicate that phenyl isothiocyanate react with complexes 1 and 4, giving the correspondent insertion products (C5H5)2Ln[SC(Ptz)NPh](THF) (Ln = Yb(9), Y(10)). All these complexes were characterized by elemental analysis and spectroscopic properties. The structures of complexes 2, 5 and 9 were also determined by the X-ray single crystal diffraction analysis. All these reactions provide a new strategy for introducing a functional substituent at the nitrogen atom of phenothiazine via forming a new C–N(ring) bond.Four new organolanthanide phenothiazine complexes were synthesized, and their reactivities toward carbodiimide or isothiocyanate were investigated, indicating that carbodiimide or isothiocyanate readily mono-inserts into the lanthanide–nitrogen bonds to give the corresponding insertion products. All the reactions provide an alternative synthetic strategy for the modification of the phenothiazine ligand.
Co-reporter:Jie Zhang, Weiyin Yi, Zhenxia Chen and Xigeng Zhou
Dalton Transactions 2013 - vol. 42(Issue 16) pp:NaN5831-5831
Publication Date(Web):2013/02/11
DOI:10.1039/C3DT00014A
The dissociation of the anionic guanidinate ligand NC(NMe2)2 promoted by rare-earth metal complexes at room temperature is described. Treatment of CpLnCl2(THF)3 with two equiv. of Li[NC(NMe2)2] in THF at room temperature affords [Cp2Ln(μ-η1:η2-L2)]2 (Ln = Y; L = NC(NMe2)NC(NMe2)2) and CpLn[NC(NMe2)2](μ-η1:η2-L)2LnCp2 (Ln = Dy) in moderated yields, respectively. YCl3 reacts with three equiv. of Li[NC(NMe2)2] under the same conditions to give a trinuclear yttrium guanidinate [(Me2N)2CN]5Y3[μ-NC(NMe2)2]2(μ-η1:η2-L)2 in 63% yield. These reactions show that rare-earth metals can promote a C–N bond cleavage of the guanidine anion [NC(NMe2)2]− at room temperature. All new complexes were characterized by elemental analysis and spectroscopic properties, and their solid-state structures were determined through single-crystal X-ray diffraction analysis.
Co-reporter:Jie Zhang, Zhengxing Zhang, Zhenxia Chen and Xigeng Zhou
Dalton Transactions 2012 - vol. 41(Issue 2) pp:NaN359-359
Publication Date(Web):2011/11/14
DOI:10.1039/C1DT11383F
Two novel eight-nuclear lanthanide oxide and chloride clusters Ln8(μ-η2-L4)2(μ3-Cl)4(μ-Cl)10(μ4-O)3(THF)8 (Ln = Er(3), Dy(4); L4 = [OC{(Me)CN-2,6-iPrC6H3}2]2−) have been synthesized by the reaction of β-diketiminate rare-earth metal chlorides with oxygen, providing a new oxidation and coupling reaction of the β-diketiminate ligand.
Co-reporter:Jie Zhang, Yanan Han, Zhenxia Chen and Xigeng Zhou
Dalton Transactions 2011 - vol. 40(Issue 36) pp:NaN9100-9100
Publication Date(Web):2011/08/15
DOI:10.1039/C1DT10990A
Reaction of two equiv of [2-NCC6H4HNLi(THF)]n (1) with Cp2LnCl(THF) yields the heterobimetallic complexes Cp2Ln[κ3-(4-NH(C8N2H4)(2-NHC6H4)]Li(THF)3 (Cp = C5H5; Ln = Er (2), Y(3)), indicating an organolanthanide-mediated nucleophilic addition/cyclization of the 2-cyanobenzoamino anion to construct the 4-iminoquinazolinate dianionic ligand.
Co-reporter:Jie Zhang, Fuyan Han, Yanan Han, Zhenxia Chen and Xigeng Zhou
Dalton Transactions 2009(Issue 10) pp:NaN1811-1811
Publication Date(Web):2009/01/26
DOI:10.1039/B817776G
A salt elimination reaction of bis(cyclopentadienyl)titanium dichloride (C5H5)2TiCl2 with one equiv. of N,N′-tetramethylguanidinate lithium [LiNC(NMe2)2] proceeded in THF at room temperature to yield a bis(cyclopentadienyl)titanium mono-guanidinate chloride (C5H5)2TiCl(NC(NMe2)2) (1). However, treatment of two equiv. of LiNC(NMe2)2 with (C5H5)2TiCl2 under the same conditions resulted in the elimination of one cyclopentadienyl ring to form an unexpected mono(cyclopentadienyl)titanium bis(guanidinate) chloride (C5H5)TiCl[NC(NMe2)2]2 (2), in which only one Ti–Cl bond is broken, with the other Ti–Cl bond retained. Reaction of [(C5H5)2YCl]2 with LiNC(NMe2)2 gave the corresponding product {(C5H5)2Y[μ-η1:η2-NC(NMe2)2]}2 (3). On further investigations on the reactivity of 1–3 toward phenyl isocyanate, we found phenyl isocyanate only inserts into the Y–N(μ-Gua) bonds of 3 to yield [(C5H5)2Y(μ-η1:η2-OC(NC(NMe2)2)NPh)]2 (4). Complexes 1–4 were characterized by elemental analysis and spectroscopic properties and their solid-state structures were determined by X-ray single-crystal diffraction.
Co-reporter:Jie Zhang, Liping Ma, Yanan Han, Fuyan Han Zhengxing Zhang, Ruifang Cai, Zhenxia Chen and Xigeng Zhou
Dalton Transactions 2009(Issue 17) pp:NaN3305-3305
Publication Date(Web):2009/02/04
DOI:10.1039/B813711K
The reaction of N,N′-dicyclohexylcarbodiimide (DCCI) with [Cp2Yb(o-H2NC6H4S)]2 (Cp = C5H5) (1) forms the monomer product Cp2Yb[SC6H4NC(NHCy)2] (2), indicating that the adjacent NH2group can add to the CN double bonds of carbodiimide to construct a neutral guanidine group. When DCCI reacts with [Cp2Y(o-H2NC6H4S)]2·2THF (4), a dimer product [CpY(μ-η2:η1-SC6H4NC(NHCy)NCy)(THF)]2 (5) was isolated, through the amino group addition and cyclopentadienyl elimination. Interestingly, on treatment of 4 with one or two equivalent of iPrNCNiPr at the same conditions gave an amino group partial addition product CpY(THF)[μ-η2:η1-SC6H4NC(NHiPr)NiPr)](μ-η2:η1-SC6H4NH2)YCp2·THF (6), where only one NH2group can add to the CN double bonds of carbodiimide molecule, another one is remained. However, when we extended this reaction to the gadolinium complex, a novel co-crystalline compound {Cp2Gd[SC6H4NC(NHCy)2]}·{CpGd(THF)[μ-η2:η1-SC6H4NC(NHCy)NCy)][μ-η2:η1-SC6H4NH2]GdCp2·THF} (8) was obtained from the reaction of [Cp2Gd(o-H2NC6H4S)]2 (7) with DCCI. In order to investigate the sequence of addition and the elimination of the cyclopentadienyl group, a deprotonation reaction of the addition product has also been studied. Reaction of CpYb[SC6H4NC(NHiPr)2]2(THF) (9), formed by reaction of Cp3Yb with two equivalent of o-aminothiophenol, and subsequently with 2 equiv. of iPrNCNiPr, with one equiv. of Cp3Yb gave a cyclopentadienyl elimination product [CpYb(μ-η2:η1-SC6H4NC(NHiPr)NiPr)(THF)]2 (3). This result reveals that addition of the NH2group to carbodiimide is prior to the elimination of cyclopentadienyl group. All of new compounds have been characterized by elemental analysis and spectroscopic properties. The solid-state structures of complexes 2, and 5–9 were determined by single-crystal X-ray diffraction.
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