DUGi

Oxidative Cleavage of C=S and P=S Bonds at an AlI Center: Preparation of Terminally Bound Aluminum Sulfides

http://dugi.udg.edu/item/http:@@@@hdl.handle.net@@2072@@299009

Aquest mateix article està publicat a l’edició alemanya d’’Angewandte Chemie’ (ISSN 0044-8249, EISSN 1521-3757), 2016, vol.128, núm. 42, p. 13500–13505. DOI http://dx.doi.org/10.1002/ange.201607735

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 calculation

Financial support from the Spanish Ministerio de Economía y Competitividad in the form of grant CTQ2014-54306-P to S.F.V. is appreciated

Wiley