Titanium imido complexes of pendant arm functionalised benzamidinate ligands

C. L. Boyd, A. E. Guiducci, Stuart R. Dubberley, Ben R. Tyrrell, P. Mountford
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引用次数: 20

Abstract

Reactions of the lithiated pendant arm functionalised benzamidinates Li{Me2NCH2CH2NC(Ph)NSiMe3} and Li{Me2NCH2CH2CH2NC(Ph)NSiMe3} with the compounds [Ti(NR)Cl2(py)3] (R = tBu, 2,6-Me2C6H3, 2,6-iPr2C6H3) afforded five-coordinate [Ti(NR){Me2NCH2CH2NC(Ph)NSiMe3}Cl] 1–3 and [Ti(NR){Me2NCH2CH2CH2NC(Ph)NSiMe3}Cl] 4–6, respectively. Reaction of [Ti(NtBu){Me2NCH2CH2CH2NC(Ph)NSiMe3}Cl] 4 with C6F5NH2 gave elimination of tBuNH2 and the corresponding perfluoroarylimido complex 7. The X-ray crystal structures of [Ti(NtBu){Me2NCH2CH2NC(Ph)NSiMe3}Cl] 1 and [Ti(N-2,6-R2C6H3){Me2NCH2CH2CH2NC(Ph)NSiMe3}Cl] (R = Me 5 or iPr 6) have been determined. Reaction of either 1 or 4 with H2N-2,6-Me2C6H3 in C6D6 afforded the corresponding arylimido compounds 2 and 5, but this route is not amenable to easy scale-up. For better evaluation of the effects of the pendant NMe2 donor group in 1–6, the bis(pyridine) compound [Ti(NtBu){MeCH2CH2NC(Ph)NSiMe3}Cl(py)2] 9 was prepared from Li{MeCH2CH2NC(Ph)NSiMe3} 8 and [Ti(NtBu)Cl2(py)3]. The compounds 1–3 with two-carbon pendant arms are quite sensitive to adventitious protonation, and the X-ray crystal structures of the products of two such reactions, namely [Ti2{Me2NCH2CH2NC(Ph)N(H)SiMe3}2(NtBu)2Cl2(μ-Cl)2] 10 and [Ti2(N-2,6-C6H3Me2)2Cl2(μ-O){Me2NCH2CH2NC(Ph)N(H)SiMe3}2] 11, have been determined. Both possess amidine ligands that show interesting intramolecular N–H⋯X (X = μ-Cl or μ-O) hydrogen bonds.
垂臂功能化苯甲酰胺配体的亚胺钛配合物
锂化垂臂功能化苄胺酸盐Li{Me2NCH2CH2NC(Ph)NSiMe3}和Li{Me2NCH2CH2NC(Ph)NSiMe3}与化合物[Ti(NR)Cl2(py)3] (R = tBu, 2,6- me2c6h3, 2,6- ipr2c6h3)反应得到五坐标[Ti(NR){Me2NCH2CH2NC(Ph)NSiMe3}Cl] 1-3和[Ti(NR){Me2NCH2CH2NC(Ph)NSiMe3}Cl] 4-6。[Ti(NtBu){Me2NCH2CH2CH2NC(Ph)NSiMe3}Cl] 4与C6F5NH2反应,消除了tBuNH2和相应的全氟羰基络合物7。测定了[Ti(NtBu){Me2NCH2CH2NC(Ph)NSiMe3}Cl] 1和[Ti(n -2,6- r2c6h3){Me2NCH2CH2NC(Ph)NSiMe3}Cl] (R = me5或iPr 6)的x射线晶体结构。1或4与h2n -2,6- me2c6h3在C6D6中反应得到相应的芳基氨基化合物2和5,但该途径不容易放大。为了更好地评价1-6中挂载NMe2给体基团的作用,以Li{MeCH2CH2NC(Ph)NSiMe3} 8和[Ti(NtBu)Cl2(py)3]为原料制备了双(吡啶)化合物[Ti(NtBu){MeCH2CH2NC(Ph)NSiMe3}Cl(py)2] 9。具有两碳悬垂臂的化合物1-3对非定质子化非常敏感,测定了两个非定质子化反应产物[Ti2{Me2NCH2CH2NC(Ph)N(H)SiMe3}2(NtBu)2Cl2(μ-Cl)2] 10和[Ti2(N-2,6- c6h3me2)2Cl2(μ-O){Me2NCH2CH2NC(Ph)N(H)SiMe3}2] 11的x射线晶体结构。两者都具有酰胺配体,显示出有趣的分子内N-H⋯X (X = μ-Cl或μ-O)氢键。
本文章由计算机程序翻译,如有差异,请以英文原文为准。
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