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

Aishabibi Kassymbek; James F Britten; Denis Spasyuk; Bulat Gabidullin; Georgii I Nikonov

doi:10.1021/acs.inorgchem.9b01005

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

Inorg Chem. 2019 Jul 1;58(13):8665-8672. doi: 10.1021/acs.inorgchem.9b01005. Epub 2019 Jun 13.

Authors

Aishabibi Kassymbek¹, James F Britten², Denis Spasyuk³, Bulat Gabidullin⁴, Georgii I Nikonov¹

Affiliations

¹ Department of Chemistry , Brock University , 1812 Sir Isaac Brock Way , St. Catharines , Ontario L2S 3A1 , Canada.
² Department of Chemistry , McMaster University , Hamilton, Ontario, 1280 Main Street West , Hamilton , Ontario L8S 4M1 , Canada.
³ SM and MX Crystallography , Canadian Light Source Inc. , 44 Innovation Boulevard , Saskatoon , Saskatchewan S7N 2 V3 , Canada.
⁴ X-ray Core Facility, Faculty of Science , University of Ottawa , 150 Louis Pasteur , Ottawa , Ontario K1N 6N5 , Canada.

PMID: 31194533
DOI: 10.1021/acs.inorgchem.9b01005

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.