Abstract:
The bimetallic complex [Cl2Pt(bpym)Re(CO)(3)Cl] (4) (where bpym
denotes 2,2’-bipyrimidine) has been prepared along with the
corresponding monometallic precursors and the dithiolate derivatives
with bdt(2-) (1,2-benzene-dithiolate) and mnt(2-)
(1,2-maleonitrile-dithiolate). The compounds have been characterized
using elemental analysis, NMR, FTIR, UV-Vis and cyclic voltammetry
methods. DFT and TD-DFT calculations on all the complexes under study
allow us to correlate geometries and electronic structures. The
theoretical studies of the dithiolate bimetallic complexes assigned the
main band in the UV-Vis spectrum as a mixed metal ligand to ligand
charge transfer transition (MML’CT), analogous to
[M(diimine)(dithiolate)] complexes, with the former red shifted due to
the presence of the Re(CO)(3)Cl moiety. Moreover coordination of the
dithiolate ligand to the bimetallic complex 4 influences not only the
energy, but also the nature of HOMO orbital altering it from Re(CO)(3)Cl
to Pt/bdt character. (C) 2012 Elsevier Ltd. All rights reserved.
