Carbon–hydrogen cleavage reactions of some trimethyl- and triethyl-phosphine complexes of osmium

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Abstract
A new type of metallation reaction is reported in which the complexes Os3(CO)11(PR3) or Os3(CO)10(PR3)2(R = Me or Et) on heating in refluxing n-nonane give the derivatives H2Os3(R2PCX)(CO)9 or H2Os3(R2PCX)(CO)8(PR3) where X = H or Me. The ligands R2PCX bridge the three metal atoms and the nonacarbonyl complexes show rapid exchange between hydrides as well as between R-groups. Isomerism observed for H2Os3(Me2PCH)(CO)8(PMe3) is probably due to the PMe3 occupying different co-ordination positions.