The synthesis, spectroscopic characterisation, crystal and molecular structure of the [ReCl3(NO)(OPPh3)(pyz)] complex. DFT calculations for [ReCl3(NO)(OPPh3)(pyz)] and [ReCl3(NO)(OPPh3) (PPh3)]

摘要

A new rhenium nitrosyl - [ReCl3(NO)(OPPh3)(pyz)] - has been obtained by two different routes: (i) in the substitution reaction of [ReCl(NO)(OPPh3)(PPh3)] with pyrazine, and (ii) in the nitrosylation reaction of [ReOCl3(PPh3)(2)] by gaseous nitric oxide in the presence of an excess of pyrazine. The crystal, molecular and electronic structure of the [ReCl3(NO)(OPPh3)(pyz)] complex has been determined. The geometric parameters of [ReCl3(NO)(OPPh3)(pyz)] have been examined using the density functional theory (DFT) method. The UV-Vis spectrum of the pyrazine complex has been interpreted on the basis of the electronic transitions of [ReCl3(NO)(OPPh3)(pyz)] calculated with the time-dependent DFT method (TDDFT). The paper also includes the results of the DFT and TDDFT calculations for [ReCl3(NO)(OPPh3)(PPh3)]. (C) 2004 Elsevier Ltd. All rights reserved.