Co-reporter:Wei Gao, Lan Xin, Zhiqiang Hao, Guodong Li, Ji-Hu Su, Lijing Zhou and Ying Mu
Chemical Communications 2015 vol. 51(Issue 32) pp:7004-7007
Publication Date(Web):17 Mar 2015
DOI:10.1039/C5CC00582E
The BIAN ligands in Brookhart catalysts were proved to be redox-active during the catalyst activation with alkylaluminum or MAO, and the neutral catalytically active species with a radical anionic BIAN rather than the cationic ones with a neutral BIAN ligand were confirmed to be formed in the catalytic system.
Co-reporter:Zhiqiang Hao, Bin Xu, Wei Gao, Yuxi Han, Guang Zeng, Jingshun Zhang, Guanghua Li, and Ying Mu
Organometallics 2015 Volume 34(Issue 12) pp:2783-2790
Publication Date(Web):May 20, 2015
DOI:10.1021/acs.organomet.5b00247
The treatment of 2-(ArN═CH)C6H4-HNC9H6N ([NQNANIMe]H, Ar = 2,6-Me2C6H3; [NQNANIEt]H, Ar = 2,6-Et2C6H3; [NQNANIiPr]H, Ar = 2,6-iPr2C6H3) with nBuLi and CrCl3(THF)3 achieves the hetero-dinuclear complexes [NQNANIR]CrCl(μ-Cl)2Li(THF)2 (1a, R = Me; 1b, R = Et; 1c, R = iPr) or bisligated complex κ5-[NQNANIiPr]2CrCl (2c) depending on the reactant ratios used. Reactions of these ligands with nBuLi and CrCl2(THF)2 could achieve the square-pyramidal complexes [NQNANIR]CrCl(THF) (3b, R = Et; 3c, R = iPr). Complex 3c can be oxidized by alkyl chloride to dimeric complex {[NQNANIiPr]CrCl}2(μ-Cl)2 (4) through a single-electron-transfer mechanism. Similar reaction of 2-(C9H6N)N═CHC6H4-HNAr ([NQNINAMe]H, Ar = 2,6-Me2C6H3; [NQNINAEt]H, Ar = 2,6-Et2C6H3; [NQNINAiPr]H, Ar = 2,6-iPr2C6H3) with nBuLi and CrCl3(THF)3 furnishes [NQNINAR]CrCl(μ-Cl)2Li(THF)2 (5a, R = Me; 5b, R = Et; 5c, R = iPr) in high yields. However, a chromium complex with a butyl-substituted ligand, [NQBuNINAiPr]CrCl2 (6), is obtained when 2 equiv of nBuLi is used. The molecular structures of 1c, 2c, 3c, 4, 5c, and 6 are confirmed by X-ray crystallography. Upon activation with MAO, the Cr(III) complexes (1a–1c, 4, and 5a–5c) show moderate catalytic activities (50 to 218 kg of PE·mol(Cr)−1·h–1) in ethylene polymerization, whereas the Cr(II) complexes 2c, 3b, and 3c are inert under the same conditions.
Co-reporter:Zhiqiang Hao, Nan Yang, Wei Gao, Lan Xin, Xuyang Luo, Ying Mu
Journal of Organometallic Chemistry 2014 749() pp: 350-355
Publication Date(Web):
DOI:10.1016/j.jorganchem.2013.10.020
Co-reporter:Zhiqiang Hao, Yuxi Han, Wei Gao, Lan Xin, Ying Mu
Polyhedron 2014 Volume 83() pp:236-241
Publication Date(Web):24 November 2014
DOI:10.1016/j.poly.2014.08.003
Reactions of the ortho-C6H4(NHAr)-(CHNAr) with nBuLi and subsequent addition of FeCl2 afford the anilido-aldimine Fe(II) complexes [(ArNCHC6H4-NAr)Fe]2(μ-Cl)2 (Ar = 2,6-Me2C6H3 (1a); Ar = 2,6-Et2C6H3 (1b)), and (ArNCHC6H4-NAr)Fe(μ-Cl)2Li(THF)2 (Ar = 2,6-iPr2C6H3 (1c)). Similarly, reactions of the 2-(ArNC(H))C6H4-HNC9H6N with nBuLi and FeCl2 give the N,N,N-tridentate iron complexes {[2-(ArNC(H))C6H4-NC9H6N]Fe}2(μ-Cl)2 (Ar = 2,6-Me2C6H3 (2a), 2,6-Et2C6H3 (2b), and 2,6-iPr2C6H3 (2c)). The X-ray diffraction analysis reveals that 1a and 1b are dimeric complexes and 1c is hetero-binuclear complex. Fe(II) atoms in these complexes are all in a distorted tetrahedral geometry. Complex 2c was confirmed to be a dimeric complex with the iron atom in a trigonal bipyramidal geometry. Complexes 1a–1c show moderate activities in ATRP of MMA in the presence of benzyl chloride (BnCl). While complexes 2a–2c are inert under the same condition.Several Fe(II) complexes supported by anilindo-imine and quinolinyl anilindo-imine ligands were synthesized and tested in iron mediated ATRP polymerization of MMA.
Co-reporter:Bo Gao, Lan Xin, Wei Gao, Zhi-Qiang Hao, Xiao-Zhi Xin, Qiao-Lin Wu, Ying Mu
Polyhedron 2013 Volume 63() pp:91-95
Publication Date(Web):31 October 2013
DOI:10.1016/j.poly.2013.07.010
Reduction reactions of the phenanthrene-o-aryliminoquinone with 0.5 equiv of magnesium in tetrahydrofuran afford the bisligated magnesium complexes [Arpiq]2Mg(thf) (1a, Ar = 2,6-Me2C6H3; 1b, Ar = 2,6-iPr2C6H3). 1a can be further reduced by magnesium to oxygen-bridged dinuclear complex [(μ-O)ArpiqMg(thf)2]2 (2). Similar reduction reactions of the N,N-bis(arylimino)phenanthrene with magnesium give bis(arylimino)phenanthrene magnesium complexes Ar1,Ar2bipMg(thf)3 (3, Ar1 = Ar2 = 2,6-Me2C6H3; 4, Ar1 = Ar2 = 2,6-iPr2C6H3; 5, Ar1 = 2,6-Me2C6H3, Ar2 = 2,6-iPr2C6H3). All the complexes were well characterized and the molecular structures of 1b, 2, 3, and 5 were established by X-ray diffraction analysis.Several Mg complexes supported by phenanthrene imine derivative ligands were synthesized and structurally characterized.
Co-reporter:Lei Zhang, Xuyang Luo, Wei Gao, Jingshun Zhang, and Ying Mu
Organometallics 2013 Volume 32(Issue 21) pp:6277-6285
Publication Date(Web):October 9, 2013
DOI:10.1021/om400562p
A series of tridentate anilido-imine [N,N,O] ligands 2-(2-(R12-2,6-C6H3NH)C6H4)HC═N(4-tBu-6-R2-C6H2OH) [R1 = Me, R2 = tBu (LaH2); R1 = Et, R2 = tBu (LbH2); R1 = iPr, R2 = tBu (LcH2); R1 = Me, R2 = Ad (LdH2); R1 = Et, R2 = Ad (LeH2); R1 = iPr, R2 = Ad (LfH2)] were synthesized and characterized. Reaction of the free ligand LdH2 with TiCl4 in toluene at low temperature affords the zwitterionic complex Ld+H2Ti–Cl4 (1d). The zwitterionic complex can be dissolved in THF to form THF-solvated complex 1d′. Heating 1d in toluene at 40 °C affords the neutral complex LdHTiCl3 (2d) by losing a HCl. Complex 2d can be fully converted to the final complex LdTiCl2 (3d) at 140 °C under vacuum by losing another HCl. Complexes 3a–3c, 3e, and 3f were also synthesized in high yields in the same one-pot procedure. All complexes were characterized by 1H and 13C NMR spectroscopy, and the molecular structures of 1d′, 3b, 3d, and 3e were determined by single-crystal X-ray diffraction analysis. The titanium centers in complexes 3b, 3d, and 3e are five-coordinated with a geometry situated between trigonal bipyramid and square pyramid. Upon activation with alkylaluminum and Ph3C+B(C6F5)4–, complexes 3a–3f exhibit moderate catalytic activity for ethylene polymerization.
Co-reporter:Dr. Jingshun Zhang;Zhiqiang Hao;Dr. Wei Gao;Lan Xin;Lei Zhang ; Ying Mu
Chemistry – An Asian Journal 2013 Volume 8( Issue 9) pp:2079-2087
Publication Date(Web):
DOI:10.1002/asia.201300581
Abstract
A series of NCO/NCS pincer precursors, 3-(Ar2OCH2)-2-Br-(Ar1NCH)C6H3 ((Ar1NCOAr2)Br, 3a, 3b, 3c, 3d) and 3-(2,6-Me2C6H3SCH2)-2-Br-(Ar1NCH)C6H3 ((Ar1NCSMe)Br, 4a and 4b) were synthesized and characterized. The reactions of [Ar1NCOAr2]Br/ [Ar1NCSMe]Br with nBuLi and the subsequent addition of the rare-earth-metal chlorides afforded their corresponding rare-earth-metal–pincer complexes, that is, [(Ar1NCOAr2)YCl2(thf)2] (5a, 5b, 5c, 5d), [(Ar1NCOAr2)LuCl2(thf)2] (6a, 6d), [(Ar1NCOAr2)GdCl2(thf)2] (7), [{(Ar1NCSMe)Y(μ-Cl)}2{(μ-Cl)Li(thf)2(μ-Cl)}2] (8, 9), and [{(Ar1NCSMe)Gd(μ-Cl)}2{(μ-Cl)Li(thf)2(μ-Cl)}2] (10, 11). These diamagnetic complexes were characterized by 1H and 13C NMR spectroscopy and the molecular structures of compounds 5a, 6a, 7, and 10 were well-established by X-ray diffraction analysis. In compounds 5a, 6a, and 7, all of the metal centers adopted distorted pentagonal bipyramidal geometries with the NCO donors and two oxygen atoms from the coordinated THF molecules in equatorial positions and the two chlorine atoms in apical positions. Complex 10 is a dimer in which the two equal moieties are linked by two chlorine atoms and two ClLiCl bridges. In each part, the gadolinium atom adopts a distorted pentagonal bipyramidal geometry. Activated with alkylaluminum and borate, the gadolinium and yttrium complexes showed various activities towards the polymerization of isoprene, thereby affording highly cis-1,4-selective polyisoprene, whilst the NCOlutetium complexes were inert under the same conditions.
Co-reporter:Bo Gao, Xuyang Luo, Wei Gao, Long Huang, Si-meng Gao, Xiaoming Liu, Qiaolin Wu and Ying Mu
Dalton Transactions 2012 vol. 41(Issue 9) pp:2755-2763
Publication Date(Web):11 Jan 2012
DOI:10.1039/C2DT11365A
Reactions of CrCl2(THF)2 with N-aryl-9,10-iminophenanthraquinone in CH2Cl2 give the monoimine chromium complexes ArIPQCrCl2(THF)2 (1, Ar = 2,6-Me2C6H3; 2, Ar = 2,6-Et2C6H3; 3, Ar = 2,6-iPr2C6H3). Molecular structures of 1 and 3 were revealed to be monomeric with the chromium atoms in distorted octahedral geometries. Similar reactions of CrCl2(THF)2 with N,N-bis(arylimino)phenanthrene ligands afford the diimine complexes Ar1,Ar2BIPCrCl(μ-Cl)3Cr(THF)Ar1,Ar2BIP (4, Ar1 = Ar2 = 2,6-Me2C6H3; 5, Ar1 = Ar2 = 2,6-Et2C6H3; 6, Ar1 = Ar2 = 2,6-iPr2C6H3; 7, Ar1 = 2,6-Me2C6H3, Ar2 = 2,6-iPr2C6H3). The X-ray diffraction analysis shows that 4, 5, and 7 are chlorine-bridged dimers with each chromium atom in a distorted octahedral geometry. Upon activation with MAO, all these complexes exhibit good catalytic activities for isoprene polymerization affording polyisoprene with predominantly a cis-1,4 unit.
Co-reporter:Jingshun Zhang, Wei Gao, Xiaomei Lang, Qiaolin Wu, Lei Zhang and Ying Mu
Dalton Transactions 2012 vol. 41(Issue 32) pp:9639-9645
Publication Date(Web):15 Jun 2012
DOI:10.1039/C2DT30778B
Bis(imino)aryl NCN pincer Ni(II) complexes 2,6-(ArNCH)2C6H3NiBr (1: Ar = 2,6-Me2C6H3; 2: Ar = 2,6-Et2C6H3; 3: Ar = 2,6-iPr2C6H3) were prepared via the oxidative-addition of Ni(0)(Ph3P)4 with bis(N-aryl)-2-bromoisophthalaldimine. These nickel complexes were characterized by NMR and elemental analyses. Their solid molecular structures were established by X-ray diffraction analyses. The nickel metal centers adopt distorted square planar geometries with the bromine atoms acting as one coordinate ligands. The NCN pincer Fe(II) complexes 2,6-(ArNCH)2C6H3Fe(μ-Cl)2Li(THF)2 (4: Ar = 2,6-Me2C6H3; 5: Ar = 2,6-Et2C6H3; 6: Ar = 2,6-iPr2C6H3) were synthesized by lithium salt metathesis reactions of the ligand lithium salts with FeCl2. X-ray structure analyses of 4 and 5 revealed that the Fe(II) complexes are hetero-dinuclear with the iron atoms in trigonal bipyramidal environments. When activated with MAO, the nickel complexes are active for norbornene vinyl polymerization but are inert for butadiene polymerization. The Fe(II) complexes show moderate activities in butadiene polymerization when activated with alkylaluminium, affording the cis-1,4 enriched polymer.
Co-reporter:Nan Yang, Lan Xin, Wei Gao, Jingshun Zhang, Xuyang Luo, Xiaoming Liu and Ying Mu
Dalton Transactions 2012 vol. 41(Issue 37) pp:11454-11463
Publication Date(Web):17 Jul 2012
DOI:10.1039/C2DT30594A
Reactions of N,N,N-tridentate quinolinyl anilido-imine ligands with AlMe3 afford mononuclear aluminum complexes {κ3-[{2-[ArNC(H)]C6H4}N(8-C9H6N)]}AlMe2 (Ar = 2,6-Me2C6H3 (1a), 2,6-Et2C6H3 (1b), 2,6-iPr2C6H3 (1c)) or dinuclear complexes AlMe3{κ1-[{2-[ArNC(H)C6H4]N(8-C9H6N)}-κ2]AlMe2 (R = 2,6-Me2C6H3 (2a), 2,6-Et2C6H3 (2b), 2,6-iPr2C6H3 (2c)) depending on the ratios of reactants used. Similar reactions of ZnEt2 with these ligands give the monoligated ethyl zinc complexes {κ3-[{2-[ArNC(H)]C6H4}N(8-C9H6N)]}ZnEt (Ar = 2,6-Me2C6H3 (3a), 2,6-Et2C6H3 (3b), 2,6-iPr2C6H3 (3c)) or bisligated complexes {κ3-[{2-[ArNC(H)]C6H4}N(8-C9H6N)]}Zn{κ2-[{2-[ArNC(H)]C6H4}N(8-C9H6N)]} (Ar = 2,6-Me2C6H3 (4a), 2,6-Et2C6H3 (4b), 2,6-iPr2C6H3 (4c)). These complexes were well characterized by NMR and the structures of 1a, 2a, 2c, 3b and 4c were confirmed by X-ray diffraction analysis. The aluminum and zinc complexes were tested to initiate lactide polymerization in which the zinc complexes show moderate to high activities in the presence of benzyl alcohol.
Co-reporter:Bo Gao, Wei Gao, Qiaolin Wu, Xuyang Luo, Jingshun Zhang, Qing Su, and Ying Mu
Organometallics 2011 Volume 30(Issue 20) pp:5480-5486
Publication Date(Web):September 26, 2011
DOI:10.1021/om200733e
Treatment of the bis(arylimino)acenaphthene (BIAN) ligands with CrCl2(THF)2 in THF affords mononuclear complexes of ArBIANCrCl2(THF)2 (3a, Ar = 2-iPrC6H4; 3b, Ar = 2,6-Me2C6H3) and chlorine-bridging dinuclear complexes ArBIANCrCl(μ-Cl)3Cr(THF)ArBIAN (3c, Ar = 2,6-Et2C6H3; 3d, Ar = 2,6-iPr2C6H3). The molecular structures of 3b–3d were characterized by X-ray diffraction analysis, and all the chromium atoms are in octahedral geometries. Similar reactions of N-(arylimino)acenaphthenones with CrCl2(THF)2 afford the dinuclear chromium complexes with 1,1′-bis(2-aryliminoacenaphthene-1-olate) tetradentate ligands ArBIAOCr2Cl4(THF)2 (4b, Ar = 2,6-Me2C6H3; 4c, Ar = 2,6-Et2C6H3) via a pinacol cross-coupling reaction. Upon activation with MAO, these complexes show moderate-to-high activities in butadiene and isoprene polymerization, affording a cis-1,4-enriched polymer.
Co-reporter:Zhizhou Liu, Wei Gao, Xiaoming Liu, Xuyang Luo, Dongmei Cui, and Ying Mu
Organometallics 2011 Volume 30(Issue 4) pp:752-759
Publication Date(Web):January 24, 2011
DOI:10.1021/om1009236
Reactions of 2,6-(ArN═CH)2C6H3Li with CrCl2(THF)2 afford two trinuclear bis(imino)aryl NCN pincer Cr(II) complexes {[2,6-(ArN═CH)2C6H3]Cr(μ-Cl)2}2Cr [Ar = 2,6-Me2C6H3 (1a), 2,6-Et2C6H3 (1b)], and a mononuclear bis(imino)aryl NCN pincer Cr(II) complex [2,6-(ArN═CH)2C6H3]Cr(μ-Cl)2Li(THF)2 [Ar = 2,6-iPr2C6H3 (1c)], respectively. Similar reactions of 2,6-(ArN═CH)2C6H3Li with CrCl3(THF)3 produce only mononuclear bis(imino)aryl NCN pincer Cr(III) complexes [2,6-(ArN═CH)2C6H3]CrCl2(THF) [Ar = 2,6-Me2C6H3 (2a), 2,6-Et2C6H3 (2b), 2,6-iPr2C6H3 (2c)]. X-ray crystallographic analysis reveals that the terminal Cr(II) atoms in 1a and 1b and the Cr(II) atom in 1c possess a distorted trigonal bipyramidal coordination environment with the Cipso atom of the pincer ligand and two chloride atoms in the equator and the two imine nitrogen atoms in the apical positions, while the Cr(III) complexes 2a, 2b, and 2c all adopt a distorted octahedral geometry around the chromium metal. Upon activation with trialkylaluminum and [Ph3C]+[B(C6F5)4]−, the Cr(III) complexes show high catalytic activity for isoprene polymerization and afford polyisoprene with predominately trans-1,4 units, whereas the Cr(II) complexes are inert under the same conditions.
Co-reporter:Zhizhou Liu, Wei Gao, Jingshun Zhang, Dongmei Cui, Qiaolin Wu, and Ying Mu
Organometallics 2010 Volume 29(Issue 22) pp:5783-5790
Publication Date(Web):October 6, 2010
DOI:10.1021/om100344p
Reactions of 2,6-(ArN═CH)2C6H3Li with AlEt2Cl afford a number of NCN pincer aluminum complexes (2,6-(ArN═CH)2C6H3)AlEt2 (Ar = Ph (1), 2,6-Me2C6H3 (2), 2,6-Et2C6H3 (3), 2,6-iPr2C6H3 (4)). Similar reactions of 2,6-(ArN═CH)2C6H3Li with ZnEtCl produce bisligated zinc complexes (2,6-(ArN═CH)2C6H3)2Zn (Ar = Ph (5), 2,6-Me2C6H3 (6), 2,6-Et2C6H3 (7)) and monoligated NCN pincer zinc complex (2,6-(ArN═CH)2C6H3)ZnEt (Ar = 2,6-iPr2C6H3 (8)). All complexes were characterized by 1H and 13C NMR spectroscopy, and the molecular structures of complexes 3, 4, 6, 7, and 8 were determined by X-ray crystallography. The X-ray diffraction analysis reveals that both complexes 3 and 4 adopt a distorted trigonal-bipyramidal geometry around the aluminum central metal with three carbon atoms in the equator and the two imine nitrogen atoms in the apical positions. Complexes 6 and 7 adopt a distorted tetrahedral geometry around their zinc metal centers, while complex 8 adopts a square-planar geometry around its metal center. All these Al and Zn complexes are efficient initiators for l-lactide ring-opening polymerization in the presence of benzyl alcohol, and the polymerization reaction takes place in an immortal manner. The productivity of the Zn complexes is generally higher than that of the Al complexes under similar conditions.
Co-reporter:Zhiqiang Hao, Anjie Ma, Bin Xu, Wei Gao, Ying Mu
Polyhedron (18 April 2017) Volume 126() pp:
Publication Date(Web):18 April 2017
DOI:10.1016/j.poly.2017.01.018
Several copper(II) complexes bearing bidentate anilido-imine ligands [(Ar′NCHC6H4-NAr)Cu]2(μ-Cl)2 (Ar = Ar′ = 2,6-Me2C6H3 (1a); Ar = Ar′ = 2,6-Et2C6H3 (1b); Ar = 3,5-(CF3)2C6H3, Ar′ = 2,6-iPr2C6H3 (1d); Ar = p-OMeC6H4, Ar′ = 2,6-iPr2C6H3 (1e)), (Ar′NCHC6H4-NAr)CuCl (Ar = Ar′ = 2,6-iPr2C6H3 (1c)), and that bearing tridentate quinolinyl anilido-imine ligand (2,6-iPr2C6H3NCHC6H4-NAr)CuCl (Ar = 8-quinolinyl (1f)) were synthesized via reactions of the corresponding ligands with nBuLi and subsequent in-situ addition of CuCl2. The X-ray diffraction analysis revealed that 1a and 1d are dinuclear, while 1f with N,N,N-tridentate ligand is in monomeric form. In the presence of 2,2′-azobisisobutyronitrile (AIBN), these well-defined complexes showed moderate to high activities in reverse ATRP of styrene. High conversions up to 86.5% were obtained and polymers with controllable molecular weight and relatively narrow polydispersity were produced.Several copper complexes supported by bidentated and tridentated anilido-imine ligands were synthesized and used as catalysts for reverse ATRP of styrene.
Co-reporter:Bin Xu, Anjie Ma, Teng Jia, Zhiqiang Hao, Wei Gao and Ying Mu
Dalton Transactions 2016 - vol. 45(Issue 44) pp:NaN17973-17973
Publication Date(Web):2016/10/11
DOI:10.1039/C6DT03572H
Treatments of N-aryl-phenanthren-o-iminoquinone (aryl = 2,6-Me2C6H3 (MeL); 2,6-iPr2C6H3 (iPrL)) with iron powder in THF at 75 °C generate complexes [η2L]2Fe[η1LH] (1a, L = MeL; 1b, L = iPrL) in moderate yields. The X-ray crystallography analysis reveals that the molecule of 1b consists of a Fe(III) center coordinated by three phenanthren-o-iminosemiquinone ligands, two of which are in an η2 fashion while the remaining one is in an η1 fashion. The analysis of the bond parameters of ligands indicates that the η2-fashioned ligands are radical anions and the η1-fashioned one is in an aminephenolato form. Reactions of MeL and iPrL with FeCl2 in THF produce Fe(III) complexes [L]2FeCl (2a, L = MeL; 2b, L = iPrL) with the two ligands in the radical anionic form. However, similar reactions of PIQ ligands with FeCl2 in CH2Cl2 yield ion-pair complexes {[L]2FeCl}+[FeCl4]− (3a, L = MeL; 3b, L = iPrL), in which the iron center chelated by two neutral ligands can be formulated as Fe(II). Reduction of 2b with sodium provides a salt-type complex [iPrL2−]2Fe(II)Na2 (4), in which a high spin Fe(II) atom is ligated by two amidophenolate ligands, and the sodium atoms attached to the oxygen atoms of ligands are η3-coordinated by the aryl ring in amido moieties.
Co-reporter:Wei Gao, Lan Xin, Zhiqiang Hao, Guodong Li, Ji-Hu Su, Lijing Zhou and Ying Mu
Chemical Communications 2015 - vol. 51(Issue 32) pp:NaN7007-7007
Publication Date(Web):2015/03/17
DOI:10.1039/C5CC00582E
The BIAN ligands in Brookhart catalysts were proved to be redox-active during the catalyst activation with alkylaluminum or MAO, and the neutral catalytically active species with a radical anionic BIAN rather than the cationic ones with a neutral BIAN ligand were confirmed to be formed in the catalytic system.
Co-reporter:Bo Gao, Xuyang Luo, Wei Gao, Long Huang, Si-meng Gao, Xiaoming Liu, Qiaolin Wu and Ying Mu
Dalton Transactions 2012 - vol. 41(Issue 9) pp:NaN2763-2763
Publication Date(Web):2012/01/11
DOI:10.1039/C2DT11365A
Reactions of CrCl2(THF)2 with N-aryl-9,10-iminophenanthraquinone in CH2Cl2 give the monoimine chromium complexes ArIPQCrCl2(THF)2 (1, Ar = 2,6-Me2C6H3; 2, Ar = 2,6-Et2C6H3; 3, Ar = 2,6-iPr2C6H3). Molecular structures of 1 and 3 were revealed to be monomeric with the chromium atoms in distorted octahedral geometries. Similar reactions of CrCl2(THF)2 with N,N-bis(arylimino)phenanthrene ligands afford the diimine complexes Ar1,Ar2BIPCrCl(μ-Cl)3Cr(THF)Ar1,Ar2BIP (4, Ar1 = Ar2 = 2,6-Me2C6H3; 5, Ar1 = Ar2 = 2,6-Et2C6H3; 6, Ar1 = Ar2 = 2,6-iPr2C6H3; 7, Ar1 = 2,6-Me2C6H3, Ar2 = 2,6-iPr2C6H3). The X-ray diffraction analysis shows that 4, 5, and 7 are chlorine-bridged dimers with each chromium atom in a distorted octahedral geometry. Upon activation with MAO, all these complexes exhibit good catalytic activities for isoprene polymerization affording polyisoprene with predominantly a cis-1,4 unit.
Co-reporter:Nan Yang, Lan Xin, Wei Gao, Jingshun Zhang, Xuyang Luo, Xiaoming Liu and Ying Mu
Dalton Transactions 2012 - vol. 41(Issue 37) pp:NaN11463-11463
Publication Date(Web):2012/07/17
DOI:10.1039/C2DT30594A
Reactions of N,N,N-tridentate quinolinyl anilido-imine ligands with AlMe3 afford mononuclear aluminum complexes {κ3-[{2-[ArNC(H)]C6H4}N(8-C9H6N)]}AlMe2 (Ar = 2,6-Me2C6H3 (1a), 2,6-Et2C6H3 (1b), 2,6-iPr2C6H3 (1c)) or dinuclear complexes AlMe3{κ1-[{2-[ArNC(H)C6H4]N(8-C9H6N)}-κ2]AlMe2 (R = 2,6-Me2C6H3 (2a), 2,6-Et2C6H3 (2b), 2,6-iPr2C6H3 (2c)) depending on the ratios of reactants used. Similar reactions of ZnEt2 with these ligands give the monoligated ethyl zinc complexes {κ3-[{2-[ArNC(H)]C6H4}N(8-C9H6N)]}ZnEt (Ar = 2,6-Me2C6H3 (3a), 2,6-Et2C6H3 (3b), 2,6-iPr2C6H3 (3c)) or bisligated complexes {κ3-[{2-[ArNC(H)]C6H4}N(8-C9H6N)]}Zn{κ2-[{2-[ArNC(H)]C6H4}N(8-C9H6N)]} (Ar = 2,6-Me2C6H3 (4a), 2,6-Et2C6H3 (4b), 2,6-iPr2C6H3 (4c)). These complexes were well characterized by NMR and the structures of 1a, 2a, 2c, 3b and 4c were confirmed by X-ray diffraction analysis. The aluminum and zinc complexes were tested to initiate lactide polymerization in which the zinc complexes show moderate to high activities in the presence of benzyl alcohol.
Co-reporter:Jingshun Zhang, Wei Gao, Xiaomei Lang, Qiaolin Wu, Lei Zhang and Ying Mu
Dalton Transactions 2012 - vol. 41(Issue 32) pp:NaN9645-9645
Publication Date(Web):2012/06/15
DOI:10.1039/C2DT30778B
Bis(imino)aryl NCN pincer Ni(II) complexes 2,6-(ArNCH)2C6H3NiBr (1: Ar = 2,6-Me2C6H3; 2: Ar = 2,6-Et2C6H3; 3: Ar = 2,6-iPr2C6H3) were prepared via the oxidative-addition of Ni(0)(Ph3P)4 with bis(N-aryl)-2-bromoisophthalaldimine. These nickel complexes were characterized by NMR and elemental analyses. Their solid molecular structures were established by X-ray diffraction analyses. The nickel metal centers adopt distorted square planar geometries with the bromine atoms acting as one coordinate ligands. The NCN pincer Fe(II) complexes 2,6-(ArNCH)2C6H3Fe(μ-Cl)2Li(THF)2 (4: Ar = 2,6-Me2C6H3; 5: Ar = 2,6-Et2C6H3; 6: Ar = 2,6-iPr2C6H3) were synthesized by lithium salt metathesis reactions of the ligand lithium salts with FeCl2. X-ray structure analyses of 4 and 5 revealed that the Fe(II) complexes are hetero-dinuclear with the iron atoms in trigonal bipyramidal environments. When activated with MAO, the nickel complexes are active for norbornene vinyl polymerization but are inert for butadiene polymerization. The Fe(II) complexes show moderate activities in butadiene polymerization when activated with alkylaluminium, affording the cis-1,4 enriched polymer.
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