Abstract
Infrared spectroscopy in the carbonyl stretching region and H NMR spectroscopy indicate that solvent (S)-coordinated acyl complexes [(CO)(S)MnCOR] form in the reactions of manganese carbonyl alkyls [(CO)MnR] with polar solvents. The extent of reaction is ethyl ≫ methyl > 2,3,4,5,6-pentamethylbenzyl > 2,4,6-trimethylbenzyl ≫ 4-methylbenzyl ~ phenyl and DMSO > DMF > pyridine > acetonitrile. The solvent-coordinated acyl complexes slowly decompose to yield, first, [(CO)Mn(COR)] and then [(CO)Mn]. Further evidence for solvent involvement in ligand-induced CO insertion reactions has been obtained from kinetic analysis of the reaction of [(CO)MnCHCHCH-4] with PPh in toluene solutions containing known amounts of polar solvents or solid promoters, such as OPPh and dibenzyl sulfoxide.
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