Thiolate-bridged heterometallic complexes of manganese and platinum: Synthesis and molecular structures of (CO)4Mn(μ-SPh)Pt(PPh3)2, (CO)3(PPh3)Mn(μ-SPh)Pt(PPh3)(CO), and (CO)3Mn(μ-SPh)Pt(PPh3)(Dppm)

Abstract

A reaction of the dimer [Mn(CO)4(SPh)]2 with (PPh3)2Pt(C2Ph2) gave the heterometallic complex (CO)4Mn(μ-SPh)Pt(PPh3)2 (I) and its isomer (CO)3(PPh3)Mn(μ-SPh)Pt(PPh3)(CO) (II). A reaction of complex I with a diphosphine ligand (Dppm) yielded the heterometallic complex (CO)3Mn(μ-SPh)Pt(PPh3)(Dppm) (III). Complexes I–III were characterized by X-ray diffraction. In complex I, the single Mn-Pt bond (2.6946(3) A) is supplemented with a thiolate bridge with the shortened Pt-S and Mn-S bonds (2.3129(5) and 2.2900(6) A, respectively). Unlike complex I, in complex II, one phosphine group at the Pt atom is exchanged for one CO group at the Mn atom. The Mn-Pt bond (2.633(1) A) and the thiolate bridge (Pt-S, 2.332(2) A; Mn-S, 2.291(2) A) are retained. In complex III, the Mn-Pt bond (2.623(1) A) is supplemented with thiolate (Pt-S, 2.341(2) A; Mn-S, 2.292(2) 0A) and Dppm bridges (Pt-P, 2.240(1)A; Mn-P, 2.245(2) A). Apparently, the Pt atom in complexes I–III is attached to the formally double bond , as in Pt complexes with olefins.