Interaction of Multiple Bonds with NacNacGa: Oxidative Cleavage vs Coupling and Cyclization

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 heteroc...

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Bibliographic Details
Published in:Inorganic chemistry 2019-07, Vol.58 (13), p.8665-8672
Main Authors: Kassymbek, Aishabibi, Britten, James F, Spasyuk, Denis, Gabidullin, Bulat, Nikonov, Georgii I
Format: Article
Language:English
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Summary: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.
ISSN:0020-1669
1520-510X
DOI:10.1021/acs.inorgchem.9b01005