Synthesis and reactivity of binuclear complexes having the Rh(μ-pz)(μ-SR)Rh framework (pz = pyrazolate, R = But, Ph)

Resumen

The formation and properties of the heterobridged complexes [Rh2(μ-pz)(μ-SPh)(COD)2] (I) (COD = 1,5-cyclo-octadiene, pz = pyrazolate) and [Rh2(μ-pz)(μ-SPh)(CO)2(PPh3)2] (II) are reported. The related heterobridged compound [Rh2(μ-pz)(μ-SBut)(CO)2{P(OMe)3}2] (III) undergoes stepwise addition of molecular iodine to yield the complexes [Rh2(μ-pz)(μ-SBut)In,(CO)2{P(OMe)3}2] [n = 2 (IV) 4 (V)]. The formation of the tetracarbonyl derivative [Rh2(μ-pz)(μ-SBut)I2(CO)4] (VI) is also reported. Reaction of the dirhodium(II) complex [Rh2(μ-pz)(μ-SBut)I2(CO)2{P(OMe)3}2] with tin(II) chloride gave the trihalostannyl derivative [Rh2(μ-pz)(μ-SBut)(SnCl2I)2(CO)2{P(OMe)3}2] (VII). Complex III reacts with mercury(II) chloride in a 1 : 1 molar ratio to give the rhodium(III)-rhodium(I) complex [Rh2(μ-pz)(μ-SBut)(μ-HgCl)Cl(CO)2{P(OMe)3}2 (VIII), resulting from the oxidative addition of HgCl2 to one metal centre. Interaction of the mixed oxidation state complex VIII with molecular iodine affords the dirhodium(III) compound [Rh2(μ-pz)(μ-SBut)(HgCl)(Cl)I2(CO)2{P(OMe)3}2] (IX). © 1992.