Addition of alkynes to a gallium bis-amido complex: imitation of transition-metal-based catalytic systems.

Acetylene, phenylacetylene, and alkylbutynoates add reversibly to (dpp-bian)Ga-Ga(dpp-bian) (dpp-bian=1,2-bis[(2,6-diisopropylphenyl)-imino]acenaphthene) to give addition products [dpp-bian(R(1)C=CR(2))]Ga-Ga[(R(2)C=CR(1))dpp-bian]. The alkyne adds across the Ga-N-C section, which results in new carbon-carbon and carbon-gallium bonds. The adducts were characterized by electron absorption, IR, and (1)H NMR spectroscopy and their molecular structures have been determined by single-crystal X-ray analysis.

Reversible addition of alkynes to gallium complex of chelating diamide ligand.

Different alkynes add reversibly to the gallium complex of the dpp-Bian dianion. The reactions proceed with addition of the alkynes across the Ga-N-C fragment resulting in carbon-carbon and carbon-gallium bonds. In the case of 3 and 4 a full elimination of the alkyne takes place at T < 100 degrees C, whereas with adducts 5 and 6 it occurs at heating to ca.

1,2-Bis(imino)acenaphthene complexes of molybdenum and nickel.

Molybdenum hexacarbonyl reacts with 1,2-bis[(2,6-diisopropylphenyl)imino]acenaphthene (, dpp-BIAN) and 1,2-bis[(trimethylsilyl)imino]acenaphthene (, tms-BIAN) in toluene to produce (dpp-BIAN)Mo(CO)(4) () and (tms-BIAN)Mo(CO)(4) (), respectively. The reaction of [CpNi(CO)](2) with yields (dpp-BIAN)NiCp (). Metathesis between Li(2)(tms-BIAN) and NiCl(2)(dppe) affords the Ni(0) complex (tms-BIAN)Ni(dppe) ().