A comprehensive investigation of the chemistry and basicity of a parent amidoruthenium complex.

trans-(DMPE)(2)Ru(H)(NH(2)) (1) dehydrogenates cyclohexadiene and 9,10-dihydroanthracene to yield benzene (or anthracene), (DMPE)(2)Ru(H)(2), and ammonia. Addition of fluorene to 1 results in the formation of the ion pair [trans-(DMPE)(2)Ru(H)(NH(3))(+)][A(-)] (A(-) = fluorenide, 4a). Complex 1 also reacts with weak acids A-H (A-H = phenylacetylene, 1,2-propadiene, phenylacetonitrile, 4-(alpha,alpha,alpha-trifluoromethyl)phenylacetonitrile, cyclobutanone, phenol, p-cresol, aniline) to form ammonia and trans-(DMPE)(2)Ru(H)(A) (7, 8, 9a, 9b, 10, 11b, 11c, 12, respectively). In the cases where A-H = phenylacetylene, cyclobutanone, aniline, phenol, and p-cresol, the reaction was observed to proceed via ion pairs analogous to 4a. Compound 1 is reactive toward even weaker acids such as toluene, propylene, ammonia, cycloheptatriene, and dihydrogen, but in these cases deuterium labeling studies revealed that only H/D exchange between A-H and the ND(2) group is observed, rather than detectable formation of ion pairs or displacement products. Addition of triphenylmethane to 1 results in the formation of an equilibrium mixture of 1, triphenylmethane, and the ruthenium/triphenylmethide ion pair 4h. If the energetics of ion-pair association are ignored, this result indicates that the basicity of 1 is similar to that of triphenylmethide. All these observations support the conclusion that the NH(2) group in amido complex 1 is exceptionally basic and as a result prefers to abstract a proton rather than a hydrogen atom from a reactive C-H bond. The energetics and mechanism of these proton-transfer and -exchange reactions are analyzed with the help of DFT calculations.