Fluorocarbon-bridged ditertiary phosphine derivatives of rhodium carbonyl halides

Abstract
The ditertiary phosphines, [Formula: see text] (n = 1,2) react with [Rh(CO)2X]2 (X = Cl, Br) via unsymmetrical cleavage of the halide bridges to give ionic complexes [(P—P)2Rh]+ [cis-(CO)2RhX2]−. However the diarsine, [Formula: see text] (ffars) reacts in an anomalous manner to give the neutral dimer, [(ffars)Rh(CO)Cl]2. With an excess of the phosphines, (n = 1, 2 or 3) the ionic complexes [(P—P)2Rh]+Cl− are obtained. The physical and spectroscopic properties of the new compounds and the tendency of the ions, [(P—P)2Rh]+, not to undergo facile oxidative-addition reactions are discussed.

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