Oxidative-addition reactions on planar chloranilate rhodium systems. Crystal structure of [Rh2(µ-C6Cl2O4)Me2I2(CO)2(PPh3)2]

Abstract

The binuclear chloranilate complexes [Rh₂(µ-C₆Cl₂O₄)L₄]{L = CO 1 or CNR (R = toluene-p-sulfonylmethyl)2, L₄=(CO)₂(CNR)₂3, (CO)₂(PPh₃)₂4 or (CO)₂[P(OMe)₃]₂5} have been prepared and oxidative addition of the electrophiles MeI and I₂ investigated. Addition of XI (X = Me or I) to compounds 4 and 5, in a Rh : XI = 1 : 1 molar ratio, led to the symmetrical complexes [Rh₂(µ-C₆Cl₂O₄)X₂I₂(CO₂)(PR₃)₂](X = Me, R = Ph 6; X = I, R = Ph 7; X = I, R = OMe 8). Interaction of 4 and 5 with 1 mol of XI (X = Me or I) gave equimolecular mixtures of Rh^I₂ and Rh^III₂ systems. The crystal structure of 6 has been determined by X-ray diffraction methods.