Synthesis, Structures, and Reactions of Coordinatively Unsaturated Trinuclear Ruthenium Polyhydrido Complexes, [{Ru(C5Me5)}3(.MU.-H)6](Y) (Y=BF4, CF3SO3, 1/2(SO4), C6H5CO2, CH3CO2, B(C6H5)4, PF6) and [{Ru(C5Me5)}3(.MU.-H)3(.MU.3-H)2]
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Cationic triruthenium hexahydrido complexes, [{Ru(C<SUB>5</SUB>Me<SUB>5</SUB>)}<SUB>3</SUB>(μ-H)<SUB>6</SUB>](Y) (Y = BF<SUB>4</SUB>, CF<SUB>3</SUB>SO<SUB>3</SUB>, 1/2(SO<SUB>4</SUB>), C<SUB>6</SUB>H<SUB>5</SUB>CO<SUB>2</SUB>, CH<SUB>3</SUB>CO<SUB>2</SUB>), have been synthesized by the reaction of diruthenium tetrahydride [{Ru(C<SUB>5</SUB>Me<SUB>5</SUB>)}<SUB>2</SUB>(μ-H)<SUB>4</SUB>] with the corresponding acid, HBF<SUB>4</SUB>, CF<SUB>3</SUB>CO<SUB>2</SUB>H, H<SUB>2</SUB>SO<SUB>4</SUB>, C<SUB>6</SUB>H<SUB>5</SUB>CO<SUB>2</SUB>H, and CH<SUB>3</SUB>CO<SUB>2</SUB>H. The trimeric structure of these complexes has been confirmed by a crystallographic study of [{Ru(C<SUB>5</SUB>Me<SUB>5</SUB>)}<SUB>3</SUB>(μ-H)<SUB>6</SUB>](PF<SUB>6</SUB>). The treatment of [{Ru(C<SUB>5</SUB>Me<SUB>5</SUB>)}<SUB>3</SUB>(μ-H)<SUB>6</SUB>](Y) with CH<SUB>3</SUB>ONa in methanol selectively afforded a neutral trinuclear pentahydrido complex, [{Ru(C<SUB>5</SUB>Me<SUB>5</SUB>)}<SUB>3</SUB>(μ-H)<SUB>3</SUB>(μ<SUB>3</SUB>-H)<SUB>2</SUB>], which underwent an intermolecular H/D exchange reaction with benzene-<I>d</I><SUB>6</SUB>, toluene-<I>d</I><SUB>8</SUB>, or <I>o</I>-xylene-<I>d</I><SUB>10</SUB> to give [{Ru(C<SUB>5</SUB>Me<SUB>5</SUB>)}<SUB>3</SUB>(μ-D)<SUB>3</SUB>(μ<SUB>3</SUB>-D)<SUB>2</SUB>] as the result of arene C–H bond activation via an η<SUP>2</SUP>-arene intermediate complex. A cationic hydrido complex, [{Ru(C<SUB>5</SUB>Me<SUB>5</SUB>)}<SUB>3</SUB>(μ-H)<SUB>6</SUB>](Y), having a carboxylate as a counter anion was equilibrated with [{Ru(C<SUB>5</SUB>Me<SUB>5</SUB>)}<SUB>3</SUB>(μ-H)<SUB>3</SUB>(μ<SUB>3</SUB>-H)<SUB>2</SUB>] in solution, and the equilibrium constant depended on the counter anion. An X-ray diffraction study showed that [{Ru(C<SUB>5</SUB>Me<SUB>5</SUB>)}<SUB>3</SUB>(μ-H)<SUB>3</SUB>(μ<SUB>3</SUB>-H)<SUB>2</SUB>] has a triangular reaction field surrounded by three C<SUB>5</SUB>Me<SUB>5</SUB> ligands. The reaction of [{Ru(C<SUB>5</SUB>Me<SUB>5</SUB>)}<SUB>3</SUB>(μ-H)<SUB>3</SUB>(μ<SUB>3</SUB>-H)<SUB>2</SUB>] with 1 equiv of O<SUB>2</SUB> proceeded with the retention of the Ru<SUB>3</SUB> framework to yield an 80/20 mixture of a mono-μ<SUB>3</SUB>-oxo complex [{Ru(C<SUB>5</SUB>Me<SUB>5</SUB>)}<SUB>3</SUB>(μ-H)<SUB>3</SUB>(μ<SUB>3</SUB>-O)] and a di-μ<SUB>3</SUB>-oxo complex [{Ru(C<SUB>5</SUB>Me<SUB>5</SUB>)}<SUB>3</SUB>(μ-H)<SUB>3</SUB>(μ<SUB>3</SUB>-O)<SUB>2</SUB>]. A novel trinuclear μ<SUB>3</SUB>-iodo-tetra-μ-hydrido complex, [{Ru(C<SUB>5</SUB>Me<SUB>5</SUB>)}<SUB>3</SUB>(μ<SUB>3</SUB>-H)(μ-H)<SUB>3</SUB>(μ<SUB>3</SUB>-I)] was formed upon the treatment of [{Ru(C<SUB>5</SUB>Me<SUB>5</SUB>)}<SUB>3</SUB>(μ-H)<SUB>3</SUB>(μ<SUB>3</SUB>-H)<SUB>2</SUB>] with 1 equiv of CH<SUB>3</SUB>I in tetrahydrofuran. The treatment of [{Ru(C<SUB>5</SUB>Me<SUB>5</SUB>)}<SUB>3</SUB>(μ-H)<SUB>3</SUB>(μ<SUB>3</SUB>-H)<SUB>2</SUB>] with carbon monoxide generated a paramagnetic trinuclear tetracarbonyl complex, [{Ru(C<SUB>5</SUB>Me<SUB>5</SUB>)}<SUB>3</SUB>(μ-CO)<SUB>3</SUB>(μ<SUB>3</SUB>-CO)].
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