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Interaction of Multiple Bonds with NacNacGa: Oxidative Cleavage vs Coupling and Cyclization
Aishabibi Kassymbek1, James F Britten2, Denis Spasyuk3
1Department of Chemistry , Brock University , 1812 Sir Isaac Brock Way , St. Catharines , Ontario L2S 3A1 , Canada.
Abstract:
The reactivity of the gallium(I) compound NacNacGa (4) to a variety of unsaturated compounds has been studied. Whereas 4 proved surprisingly unreactive toward olefins, ketones, guanidines, and thioureas, it reacts with isocyanates and carbodiimides to furnish the products of coupling of two heterocumulenes. With isothiocyanate, the C═S cleavage occurs, leading to the dimer (NacNacGa)2(μ-S)(μ-CNPh) and the cyclization product NacNacGa(S2C═NPh). These compounds were characterized by multinuclear NMR spectroscopy and X-ray crystal structure analyses. Oxidative addition of S═PPh3 occurs at elevated temperatures and results in the known dimer [NacNacGa(μ-S)]2.
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