Titanium imido complexes containing 1,3,5-triazacyclohexane ligands

被引：31

作者：

Wilson, PJ

Blake, AJ

Mountford, P

Schröder, M

机构：

[1] Univ Nottingham, Sch Chem, Nottingham NG7 2RD, England

[2] Univ Oxford, Inorgan Chem Lab, Oxford OX1 3QR, England

来源：

JOURNAL OF ORGANOMETALLIC CHEMISTRY | 2000年 / 600卷 / 1-2期

基金：

英国工程与自然科学研究理事会;

关键词：

titanium; zirconium; imide; triazacyclohexane; X-ray diffraction; fluxional; benzyl;

D O I：

10.1016/S0022-328X(00)00032-2

中图分类号：

O61 [无机化学];

学科分类号：

070301 ; 081704 ;

摘要：

The syntheses of the 1,3,5-trimethyl- and tri-tert-butyl-1,3,5-triazacyclohexane-supported imido complexes [M(NR)(R'(3)tach)Cl-2] (M = Ti or Zr (NMR only); R = Bu-t or 2,6-C6H3Pr'(2); R' = Me or Bu-t) are reported, along with that of the thermally robust dibenzyl derivative [Ti(NBut)(Me(3)tach)(CH2Ph)(2)]. The tert-butylimido ligand in [Ti(NBut)(Me(3)tach)Cl-2] undergoes exchange with ArNH2 (Ar = 4-C6H3Me or 2,6-C6H3Pr'(2)) to form the corresponding arylimides [Ti(NAr)(Me(3)tach)Cl-2]. The Me(3)tach ring in [Ti(NR)(Me(3)tach)Cl-2] undergoes slow exchange with Bu(3)(t)tach or Me(3)tacn (1,4,7-trimethyl-1,4,7-triazacyclononane) to give the ring-exchanged products [Ti(NR)(Bu(3)(t)tach)Cl-2] and [Ti(NR)(Me(3)tacn)Cl-2], respectively. The complexes [Ti(NR)(Me(3)tach)X-2] (R = Bu-t or 2,6-C6H3Pr2i; X = Cl or CH2Ph) exhibit room-temperature dynamic NMR behaviour via an unusual trigonal twist of the facially coordinated Me(3)tach ligand, and the activation parameters for these processes have been measured and are discussed. The X-ray structures of [Ti(NR)(Bu(3)(t)tach)Cl-2] (R = Bu-t or 2,6-C6H3Pr2i) and [Ti(NBut)(Me(3)tach)(X)(2)] (X = Cl or CH2Ph) are reported. Me(3)tach and Bu(3)(t)tach = 1,3,5-trimethyl- and tri-tert-butyl-1,3,5-triazacyclohexane, respectively. (C) 2000 Elsevier Science S.A. All rights reserved.

引用

页码：71 / 83

页数：13

共 62 条

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