Abstract
The rhodium(I) complex [Rh(CO)(PEt3)(mnt)]− (mnt = maleonitriledithiolate) reacts with a variety of alkyl halides to form acyl complexes isolated in the presence of excess PEt3 as five-coordinate species of formula [Rh(COR)(PEt3)2(mnt)]. The structure of the complex for R = n-Pr has been determined by an X-ray analysis, and is found to be a square-based pyramid with the acyl group in the apical position. Addition of HClO4 to the rhodium(I) anion in the presence of excess PEt3 yields rhodium(III) hydride, [RhH(CO)(PEt3)2(mnt)], while addition of acid to the rhodium(I) complex in CH3CN solution with ethylene present leads slowly to formation of an acyl complex which is isolated as [Rh(COEt)(PEt3)2(mnt)] upon phosphine addition. A novel alkyl group migration from the acyl carbon to a donor S atom is also observed in monophosphine systems.
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