Rotameric transformations in the photochemistry of TpM(CO)2(η3-C3H4R), where Tp = tris(pyrazolyl)borate, M = Mo or W, and R = H or Me

被引：2

作者：

Thornley, Wyatt A. ^{[1
]}

Bitterwolf, Thomas E. ^{[1
]}

机构：

[1] Univ Idaho, Dept Chem, Moscow, ID 83843 USA

来源：

DALTON TRANSACTIONS | 2015年 / 44卷 / 17期

关键词：

ORGANOMETALLIC CONFORMATIONAL EQUILIBRIA; ALLYLIC COMPLEXES; STEREOCHEMICAL NONRIGIDITY; STATISTICAL AVERAGE; LIGANDS; APPROXIMATION; POTENTIALS; ENERGY; GAS;

D O I：

10.1039/c4dt03940h

中图分类号：

O61 [无机化学];

学科分类号：

070301 ; 081704 ;

摘要：

Low energy photolysis of TpM(CO)(2)(eta(3)-C3H4R), where Tp = tris(pyrazolyl)borate, M = Mo or W, and R = 2-H or 2-Me in PVC matrices at 85 K results in exo/gauche isomerism of the allyl ligand. This transformation comes in contrast to the behaviour observed in cyclopentadienyl analogues which undergo exo/endo isomerism. DFT computations reveal an eta(3) -->eta(1)* -->eta(3) mechanism for the allyl rotameric interconversion where the eta(1)*-allyl intermediate is generated upon MLCT excitation.

引用

页码：8007 / 8012

页数：6

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