Metal-induced B-H activation: addition of methyl acetylene carboxylates to Cp*Rh-, Cp*Ir-, (p-cymene)Ru-, and (p-cymene)Os half-sandwich complexes containing the chelating 1,2-dicarba-closo-dodecaborane-1,2-dithiolate ligand.

The reactions of the 16e half-sandwich complexes [Cp*M[S2C2(B10)H10)]] (1: M=Rh; 2: M = Ir) and [eta6-(4-isopropyltoluene)M[S2C2(B10H10)] (3: M=Ru; 4: M=Os) with both methyl acetylene monocarboxylate and dimethyl acetylene dicarboxylate were studied in order to obtain more evidence for B-H activation, ortho-metalation, and B(3,6)-substitution of the carborane cluster. In the case of rhodium, the reaction of 1 with methyl acetylene monocarboxylate led to new complexes after twofold insertion into one of the Rh-S bonds (7), and twofold insertion together with B-substitution at the carborane cage (8). In the case of iridium, the reactions of 2 with methyl acetylene monocarboxylate gave two geometrical isomers 10 and 11, in which the alkyne is inserted into one of the Ir-S bonds, followed by hydrogen transfer from the carborane via the metal to the former alkyne and formation of an Ir-B bond. Only one type each (12 and 13) of these isomers was obtained from the reactions of the ruthenium and osmium half-sandwich complexes 3 and 4. The 16e starting materials 1-4 reacted with dimethyl acetylene dicarboxylate at room temperature to give the complexes 14-17, respectively, which are formed by addition of the C=C bond to the metal center and insertion into one of the metal-sulfur bonds. The proposed structures in solution were deduced from NMR data (1H, 11B, 13C, 103Rh NMR), and X-ray structural analyses were carried out for the rhodium complexes 7 and 8.