Abstract
Thiocarbamoylphosphine sulfides 1 a-c and oxides 2 a-c are ambidentate chelating ligands which may form monomeric or dimeric complexes with carbonylmetal halides. The reaction of 1 a-c with ClMn(CO)5 and ClRe(CO)5 yields the monomeric cw-tetracarbonyl complexes 3 a-c and 4 a-c with S,S'-coordination. The phosphine oxides 2 a-c first form tetracarbonyl complexes which dimerize spontaneously under loss of CO to give the anfi-fac-tricarbonyl complexes 6 a-c and 6 a with bridging three-coordinate sulfur. On refluxing in n-hexane solution, 8 a-c and 4b, c are converted into the corresponding dimers 7 a-c and 8 b, c. Dissolving of 7 b, c in CH2Cl2 leads to re-formation of 8 b, c, the free ligands 1 b, c and inorganic manganese compounds.

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