Osmium-acyl decarbonylation promoted by Tp-mediated allenylidene abstraction: A new role of the Tp ligand

Phenylacetylene and 1,1-diphenyl-2-propyn-1-ol displace the pyridyl and ethylene ligands of OsTp{κ1-C[NC5H3Me]}(η2-CH2═CH2)(PiPr3) (1) to afford the alkynyl-vinylidene derivatives OsTp(C≡CR)(═C═CHR)(PiPr3) (Tp = hydridotris(pyrazolyl)borate; R = Ph, (2), C(OH)Ph2 (3)). Stirring of toluene solutions of 3 in the presence of neutral aluminum oxide initially produces the dehydration of the vinylidene ligand to give the alkynyl-allenylidene OsTp{C≡CC(OH)Ph2}(═C═C═CPh2)(PiPr3) (4), which subsequently undergoes a Meyer-Schuster rearrangement to yield the acyl-allenylidene OsTp{C(O)CH═CPh2}(═C═C═CPh2)(PiPr3) (5). In toluene, at 60 °C, the B–H bond of the Tp ligand of 5 abstracts the allene from the osmium coordination sphere by means of a 1,1-hydroboration of the Os–Cα double bond. As a result, the acyl decarbonylation takes place to form Os(Ph2C═C═CHTp)(CH═CPh2)(CO)(PiPr3) (6). In acetonitrile at 60 °C, the allene tautomerizes into the alkyne to afford Os(Ph2HCC≡CTp)(CH═CPh2)(CO)(PiPr3) (7). The abstraction modi...