Theoretical studies on the mechanism of the tropo-inversion of the BIPHEP-RuCl2/DPEN complex using the ONIOM method

被引：25

作者：

Yamanaka, M ^{[1
]}

Mikami, K ^{[1
]}

机构：

[1] Tokyo Inst Technol, Dept Appl Chem, Tokyo 1528552, Japan

来源：

ORGANOMETALLICS | 2002年 / 21卷 / 26期

关键词：

D O I：

10.1021/om020215c

中图分类号：

O61 [无机化学];

学科分类号：

070301 ; 081704 ;

摘要：

The mechanism of tropo-inversion of the Ru(II) complex bearing a chirally flexible biphenylphosphine (BIPHEP) ligand has been studied by the B3LYP and the ONIOM(B3LYP: HF) methods. The relative energy difference between the favorable (S)I(SS) and the less favorable (R)I(SS) pairs of BIPHEP-RuCl2/DPEN complexes is well comparable to the experimental results. The tropo-inversion of the (S)I(SS) pair to the (R)I(SS) pair is found to be achieved by solvent-assisted rotation around the biphenyl single bond and subsequent recoordination of phosphine to the Ru center. The sterically demanding phenyl groups attached to phosphorus atoms in the BIPHEP-RuCl2 moiety prevented the internal rotation without dissociation of P-Ru coordination.

引用

页码：5847 / 5851

页数：5

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