The First Carbonyl-Substituted Derivative of [Mn2(CO)6(µ-pyS)2

Abstract

Reaction of [Mn2(CO)6(μ-pyS)2] (1) with (Ph3P)2Ni(CO)2 at room temperature affords [Mn2(CO)5(PPh3)(μ-pyS)2] (3) which is the first carbonyl-substituted derivative of 1. A mononuclear complex fac-[Mn(CO)3(PPh3)(κ2-pyS)] (4) is also isolated as a minor product in this reaction. The formation of 3 allows us to propose a different mechanism operating in this reaction. A similar reaction between [Re2(CO)6(μ-pyS)2] (2) and (Ph3P)2Ni(CO)2 gives only mononuclear fac-[Re(CO)3(PPh3)(κ2-pyS)] (5). Both 4 and 5 undergo CO substitution to produce [M(CO)2(PPh3)2(κ2-pyS)] (6, M = Mn; 7, M = Re) when treated with (Ph3P)2Ni(CO)2 in boiling THF. Complex 3 also reacts with further (Ph3P)2Ni(CO)2 at room temperature to give 4 and 6. The molecular structures of 3 and 4 have been established by single crystal X-ray diffraction analyses.