摘要
Trinuclear selenolate complexes [(CO) 4 Mn(μ-SeR) 2 Ni(μ-SeR) 2 Mn(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 · 6H 2 O/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) Å, and a Ni II Mn I distance of 3.428(2) Å (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) 4 Mn(μ-SeMe) 2 Ni(μ-SeMe) 2 Mn(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 2 Pd(μ-SePh) 2 PdCl 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. © 1999 Elsevier Science S.A.