Acid-base adducts of catalytically active titanium(IV) Lewis acids

被引：11

作者：

Larsen, AO ^{[1
]}

White, PS ^{[1
]}

Gagné, MR ^{[1
]}

机构：

[1] Univ N Carolina, Dept Chem, Chapel Hill, NC 27599 USA

来源：

INORGANIC CHEMISTRY | 1999年 / 38卷 / 21期

关键词：

D O I：

10.1021/ic990473a

中图分类号：

O61 [无机化学];

学科分类号：

070301 ; 081704 ;

摘要：

A series of monomeric Lewis acid-base adducts of the Dials-Alder catalyst Ti(O-2,6-Me2C6H3)(2)Cl-2 have been synthesized from bidentate diphosphines and diamines, Ti(O-2,6-Me2C6H3)(2)Cl2L2 (L-2 dmpe, depe, dpeda, and dmeda). X-ray crystal structures of Ti(O-2,6-Me2C6H3)(2)Cl-2(dmpe) and Ti(O-2,6-Me2C6H3)(2)Cl-2(dpeda) establish a distorted octahedral coordination environment with trans-chloride ligands. Bidentate ligands that were also studied but did not form isolable complexes with the Ti(IV) Lewis acid include dppe, tmeda, and binam. Through pairwise exchange reactions a qualitative ranking of relative bidentate ligand binding strengths to the Lewis acid were obtained (dmeda greater than or equal to dpeda > dmpe greater than or equal to depe > tmeda > binam > dppe). The ranking is readily rationalized using hard-soft electronic arguments except for tmeda, which requires that unfavorable steric interactions be invoked.

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页码：4824 / 4828

页数：5

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