Repercussion of a 1,3-Hydrogen Shift in a Hydride-Osmium-Allenylidene Complex

An unusual 1,3-hydrogen shift from the metal center to the C_β atom of the C₃-chain of the allenylidene ligand in a hydride-osmium(II)-allenylidene complex is the beginning of several interesting transformations in the cumulene. The hydride-osmium(II)-allenylidene complex was prepared in two steps, starting from the tetrahydride dimer [(Os(H···H){κ³-P,O,P-[xant(P Pr₂)₂]})₂(μ-Cl)₂][BF₄]₂ (1). Complex 1 reacts with 1,1-diphenyl-2-propyn-1-ol to give the hydride-osmium(II)-alkenylcarbyne [OsHCl(≡CCH=CPh₂){κ³-P,O,P-[xant(P Pr₂)₂]}]BF₄ (2), which yields OsHCl(=C=C=CPh₂){κ³-P,O,P-[xant(P Pr₂)₂]} (3) by selective abstraction of the C_β-H hydrogen atom of the alkenylcarbyne ligand with K BuO. Complex 3 is metastable. According to results of DFT calculations, the migration of the hydride ligand to the C_β atom of the cumulene has an activation energy too high to occur in a concerted manner. However, the migration can be catalyzed by water, alcohols, and aldehydes. The resulting alkenylcarbyne-osmium(0) intermediate is unstable and evolves into a 7:3 mixture of the hydride-osmium(II)-indenylidene OsHCl(=C_IndPh){κ³-P,O,P-[xant(P Pr₂)₂]} (4) and the osmanaphthalene OsCl(C₉H₆Ph){κ³-P,O,P-[xant(P Pr₂)₂]} (5). Protonation of 4 with HBF₄ leads to the elongated dihydrogen complex [OsCl(η²-H₂)(=C_IndPh){κ³-P,O,P-[xant(P Pr₂)₂]}]BF₄ (6), while the protonation of 5 regenerates 2. In contrast to 4, complex 6 evolves to a half-sandwich indenyl derivative, [Os(η⁵-IndPh)H{κ³-P,O,P-[xant(P Pr₂)₂]}][BF₄]Cl (7). Phenylacetylene also provokes the 1,3-hydrogen shift in 3. However, it does not participate in the migration. In contrast to water, alcohols, and aldehydes, it stabilizes the resulting alkenylcarbyne to afford [Os(≡CCH=CPh₂)(η²-HC≡CPh){κ³-P,O,P-[xant(P Pr₂)₂]}]Cl (8).