title: Oxidative Cleavage of C=S and P=S Bonds at an AlICenter: Preparation of Terminally Bound Aluminum Sulfides.
abstract: The treatment of cyclic thioureas with the aluminum(I) compound NacNacAl (1; NacNac=[ArNC(Me)CHC(Me)NAr]-, Ar=2,6-Pri2C6H3) resulted in oxidative cleavage of the C=S bond and the formation of 3 and 5, the first monomeric aluminum complexes with an Al=S double bond stabilized by N-heterocyclic carbenes. Compound 1 also reacted with triphenylphosphine sulfide in a similar manner, which resulted in cleavage of the P=S bond and production of the adduct [NacNacAl=S(S=PPh3)] (8). The Al=S double bond in 3 can react with phenyl isothiocyanate to furnish the cycloaddition product 9 and zwitterion 10 as a result of coupling between the liberated carbene and PhN=C=S. All novel complexes were characterized by multinuclear NMR spectroscopy, and the structures of 5, 9, and 10 were confirmed by X-ray diffraction analysis. The nature of the Al=S bond in 5 was also probed by DFT calculations.
authors.affiliation: Department of Chemistry, Brock University, 1812 Sir Isaac Brock Way, St. Catharines, Ontario, L2S 3A1, Canada.
authors.forename: Terry
authors.initials: T
authors.lastname: Chu
authors.affiliation: Institut de Química Computacional i Catàlisi and Departament de Química, Carrer Maria Aurèlia Capmany 69, 17003, Girona, Spain.
authors.forename: Sergei F
authors.initials: SF
authors.lastname: Vyboishchikov
authors.affiliation: X-Ray Core Facility, Faculty of Science, University of Ottawa, 150 Louis Pasteur, Ottawa, Ontario, K1N 6N5, Canada.
authors.forename: Bulat
authors.initials: B
authors.lastname: Gabidullin
authors.affiliation: Department of Chemistry, Brock University, 1812 Sir Isaac Brock Way, St. Catharines, Ontario, L2S 3A1, Canada. gnikonov@brocku.ca.
authors.forename: Georgii I
authors.identifier: 0000-0001-6489-4160
authors.initials: GI
authors.lastname: Nikonov
keywords: C=S activation; DFT calculations; N-heterocyclic carbenes; aluminum sulfides; oxidative addition