MIXED METAL COMPLEXES OF GROUPS 10 AND 11 ELEMENTS - THE STRUCTURE AND PROPERTIES OF [M(MNT)(2)(AG(PR(3))(2))(2)] (M=NI, PD, PT MNT(2-)=MALEONITRILEDITHIOLATE)

摘要

The reaction of [Ag(PR(3))(2)](+) (R = Ph, Bu(n)) and [M(mnt)(2)](2-) (M = Ni, Pd, Pt; mnt(2-) = maleonitriledithiolate) gave mixed-metal complexes with the general formula of [M(mnt)(2){Ag(PR(3))(2)}(2)]. X-ray structures of [Pt(mnt)(2){Ag(PPh(3))(2)}(2)] (1), [Pd(mnt)(2){Ag(PPh(3))(2)}(2)] (2) and [Pd(mnt)(2){Ag(PBu(3)(n))(2)}(2)] (5) are similar to one another. The Ag atoms have distorted tetrahedral AgP2S2 arrangement. All complexes have M-Ag distances shorter than van der Waals contacts. Complex 1 dissociates in solution, whereas [Pt(mnt)(2){Ag(PBu(3)(n))(2)}(2)] (4) does not appreciably. UV-Vis absorption spectra of the mixed-metal complexes are not much different from those of the corresponding free [M(mnt)(2)](2-) ions. The first oxidation potential of each mixed-metal compound shifted about 0.15 V positively from that of the corresponding free [M(mnt)(2)](2-) ion. P-31 NMR chemical shift and P-Ag coupling of these mixed-metal complexes do not depend significantly on the Group 10 metal atom. [References: 21]