Thiolate-bridged Trinuclear Heterobimetallic Complexes [Cd(Aμ-SPh-4-Me)4{M(PPh3)2}2] (M = Cu, Ag) and [Sn(Aμ-SPh)6(AgPPh3)2]

Reaction of the [Me4N](2)[Cd(SPh-4-Me)(4)] with two equivalents of [M(PPh3)(2)NO3] afforded the neutral linear trinuclear complexes [Cd(mu-SPh-4-Me)(4){M(PPh3)(2)}(2)] (M = Cu 1, Ag 2) in which two [M(PPh3)(2)](+) fragments chelate with the opposite edges of a tetrahedral [Cd(SPh-4-Me)(4)](2-) moiety via the sulfur atoms of the Me-4-PhS- species. Treatment of [Sn(SPh)(4)] with two equivalents of [Ag(PPh3)(2)NO3] gave the neutral linear trinuclear complex [Sn(mu-SPh)(6)(AgPPh3)(2)] (3) that is composed of a central distorted SnS6 octahedron sharing two opposite planes with two slightly distorted AgS3P tetrahedrons. Complexes 2 and 3 are air and optically stable. Their nonlinear optical absorption and refraction were investigated under the same conditions. The nonlinear optical absorption and refraction of complex 2 were determined to be alpha (2) = 3.11 x 10(-11) m/W and n (2) = 4.15 x 10(-12) esu, respectively. The nonlinear optical absorption and refraction of complex 3 were determined to be alpha (2) = 8.36 x 10(-11) m/W and n (2) = 1.47 x 10(-11) esu, respectively.