PHOTOPHYSICAL ASPECTS OF C-H BOND ACTIVATION IN RHODIUM DICARBONYL COMPLEXES

被引：25

作者：

PURWOKO, AA ^{[1
]}

DROLET, DP ^{[1
]}

LEES, AJ ^{[1
]}

机构：

[1] SUNY BINGHAMTON,DEPT CHEM,BINGHAMTON,NY 13902

来源：

JOURNAL OF ORGANOMETALLIC CHEMISTRY | 1995年 / 504卷 / 1-2期

关键词：

RHODIUM; PHOTOCHEMISTRY; C-H BOND ACTIVATION;

D O I：

10.1016/0022-328X(95)05611-R

中图分类号：

O61 [无机化学];

学科分类号：

070301 ; 081704 ;

摘要：

The solution photochemistry of C-H bond activating CpRh(CO)(2), Cp*Rh(CO)(2) and (HBPz(3)*)Rh(CO)(2) complexes (Cp = eta(5)-C5H5; Cp* = eta(5)-C(5)Me(5); HBPz(3)*; = tris(3,5-dimethylpyrazolyl)borate) has been investigated at several excitation wavelengths. Quantitative photochemical measurements have been obtained for ligand photosubstitution and intermolecular Si-H/C-H bond activation reactions through a determination of absolute quantum efficiencies. In each complex the results reveal that the photochemistry is extremely wavelength dependent and two low lying ligand field (LF) excited states are implicated in the mechanism. Population of the upper energy LF excited state leads to effective CO dissociation and subsequent Si-H/C-H bond activation, whereas excitation into the lower energy LF excited state results in inefficient photochemistry. These experimental observations are related to the electronic absorption characteristics of the molecules and are interpreted on a photophysical scheme involving excited states with quite distinct photochemical reactivities.

引用

页码：107 / 113

页数：7

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