Reductive Hydrogenation of Sulfido-Bridged Tantalum Alkyl Complexes: A Mechanistic Insight

[Image: see text] Hydrogenolysis of a series of alkyl sulfido-bridged tantalum(IV) dinuclear complexes [Ta(η(5)-C(5)Me(5))R(μ-S)](2) [R = Me, nBu (1), Et, CH(2)SiMe(3), C(3)H(5), Ph, CH(2)Ph (2), p-MeC(6)H(4)CH(2) (3)] has led quantitatively to the Ta(III) tetrametallic sulfide cluster [Ta(η(5)-C(5)Me(5))(μ(3)-S)](4) (4) along with the corresponding alkane. Mechanistic information for the formation of the unique low-valent tetrametallic compound 4 was gathered by hydrogenation of the phenyl-substituted precursor [Ta(η(5)-C(5)Me(5))Ph(μ-S)](2), which proceeds through a stepwise hydrogenation process, disclosing the formation of the intermediate tetranuclear hydride sulfide [Ta(2)(η(5)-C(5)Me(5))(2)(H)Ph(μ-S)(μ(3)-S)](2) (5). Extending our studies toward tantalum alkyl precursors containing functional groups susceptible to hydrogenation, such as the allyl-and benzyl-substituted compounds [Ta(η(5)-C(5)Me(5))(η(3)-C(3)H(5))(μ-S)](2) and [Ta(η(5)-C(5)Me(5))(CH(2)Ph)(μ-S)](2) (2), enables alternative reaction pathways en route to the formation of 4. In the former case, the dimetallic system undergoes selective hydrogenation of the unsaturated allyl moiety, forming the asymmetric complex [{Ta(η(5)-C(5)Me(5))(η(3)-C(3)H(5))}(μ-S)(2){Ta(η(5)-C(5)Me(5))(C(3)H(7))}] (6) with only one propyl fragment. Species 2, in addition to the hydrogenation of one benzyl fragment and concomitant toluene release, also undergoes partial hydrogenation and dearomatization of the phenyl ring on the vicinal benzyl unity to give a η(5)-cyclohexadienyl complex [Ta(2)(η(5)-C(5)Me(5))(2)(μ-CH(2)C(6)H(6))(μ-S)(2)] (7). The mechanistic implications of the latter hydrogenation process are discussed by means of DFT calculations.