Chelating and ligand-transfer studies of the complexes cis-[Mn(CO)_4(SeR)_2]~-: crystal structures of heterotrinuclear [(CO)_4Mn(#mu#-SeMe)_2Ni(#mu#-SeMe)_2Mn(CO)_4] with a distorted square planar Ni~(II)-selenolate core and [PPN]_2[Cl_2Pd(#mu#-SePh)

摘要

Trinuclear selenolate complexes [(CO)_4Mn(#mu#-SeR)_2Ni(#mu#-SeR)_2Mn(CO)_4] (R = Me, Ph) containing a distorted square planar Ni(Se)_4 core have been synthesized by the reaction of Ni(NO_3)_2 centre dot 6H_2O/NiCl_2 with the chelating metalloligand cis-[PPN][Mn(CO)_4(SeR)_2] in MeCN. Their structures were elucidated on the basis of IR, UV-Vis, CV, and NMR spectra. X-ray crystallography confirmed the heterotrinuclear structure in the solid state with a Ni~(II)-Se distance of 2.331(1) A, and a Ni~(II)...Mn~I distance of 3.428(2) A (average). The dependence of geometry on electron population and the larger Ni~(II)...Mn~I distances are adopted to rationalize the construction of the complex [(CO)_4Mn(#mu#-SeMe)_2Ni(#mu#-SeMe)_2Mn(CO)_4] with a distorted square planar adopted to rationalize the construction of the complex [(CO)_4Mn(#mu#-SeMe)_2Ni(#mu#-SeMe)_2Mn(CO)_4] with a distorted square planar Ni~(II)(Se)_4 core. Further reaction of cis-[PPN][Mn(CO)_4(SePh)_2] with PdCl_2 afforded [PPN]_2[Cl_2Pd(#mu#-SePh)_2PdCl_2]. Its structure has been determined. This investigation shows that cis-[Mn(CO)_4(SeR)_2]~- serves as a chelating metalloligand and selenolate ligand-transfer reagent.