An ESR study has been made of the high nuclearity paramagnetic metal cluster anions [Rh12(CO)13(μ2-CO)10(C)2]3-, [Co13(CO)12(μ2-CO)12(C)2]4- and [Co6(CO)8(μ2-CO)6C]-. The assignment of the HOMO is based on a mixed valence model which relates the g tensor components of cluster systems to those of an appropriate conventional paramagnetic center. With this model the HOMOs of [Rh12(CO)13(μ2-CO)10(C)2]3- and of [Co13(CO)12(μ2-CO)12(C)2]4- are found to be mainly comprised of metal dz2 atomic orbitals, while for [Co6(CO)8(μ2-CO)6C]- a large overlap between d atomic orbitals and ligand orbitals is suggested. The occupation of the valence molecular orbitals deduced from the ESR data is consistent with the variations in MM bond distance observed by X-ray analysis. © 1982.
|Titolo:||ESR investigation of paramagnetic carbonyl-metal clusters of high nuclearity|
BERINGHELLI, TIZIANA (Primo)
STRUMOLO, DONATELLA (Ultimo)
|Settore Scientifico Disciplinare:||Settore CHIM/03 - Chimica Generale e Inorganica|
|Data di pubblicazione:||1982|
|Digital Object Identifier (DOI):||10.1016/S0022-328X(00)86755-8|
|Appare nelle tipologie:||01 - Articolo su periodico|