Reactions of the [K]+ salts of the [nido-7,9-C2B9H12]- anion (2) and its C-phenylated derivative [7-Ph-nido-7,9-C2B9H11]- (4) with [OsCl2(PPh3)3] (3) proceed in benzene at ambient temperature with the formation of 16-electron chlorohydrido-Os(IV) exo-nido complexes, [exo-nido-10,11-{(Ph3P)2OsHCl}-10,11-(mu-H)2-7-R-7,9-C2B9H8] (5: R = H; 6: R = Ph), along with the small amounts of the charge-compensated nido-carboranes [nido-7,9-C2B9H11PPh3] (7) and [7-Ph-nido-7,9-C2B9H10PPh3] (8) as byproducts. However, when carried out under mild heating in ethanol, the reaction of 2 with 3 selectively afforded a 16-electron dihydrido-Os(IV) exo-nido complex [exo-nido-10,11-{(Ph3P)2OsH2}-10,11-(mu-H)2-7,9-C2B9H9] (9). Structures of both complexes 5 and 9 have been confirmed by single-crystal X-ray diffraction studies, which revealed that nido-carboranes in these species function as a bidentate dicarbollide ligands [7-R-nido-7,9-C2B9H10]2- linked to the Os(IV) center via two B-H.
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