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

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

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

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

© Angewandte Chemie International Edition, 2016, vol. 55, núm. 42, p. 13306-13311

Wiley

Author: Chu, Terry
Vyboishchikov, Sergei F.
Gabidullin, Bulat
Nikonov, Georgii I.
Date: 2016 October 10
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 calculation
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
Financial support from the Spanish Ministerio de Economía y Competitividad in the form of grant CTQ2014-54306-P to S.F.V. is appreciated
Format: application/pdf
ISSN: 1433-7851 (versió paper)
1521-3773 (versió electrònica)
Document access: http://hdl.handle.net/10256/13589
Language: eng
Publisher: Wiley
Collection: MINECO/PE 2015-2017/CTQ2014-54306-P
Reproducció digital del document publicat a: http://dx.doi.org/10.1002/anie.201607735
Articles publicats (D-Q)
Is part of: © Angewandte Chemie International Edition, 2016, vol. 55, núm. 42, p. 13306-13311
Rights: Tots els drets reservats
Subject: C=S activation
N-heterocyclic carbenes
oxidative addition
Sulfat d’alumini
Aluminum sulfate
Funcional de densitat, Teoria del
Density functionals
Title: Oxidative Cleavage of C=S and P=S Bonds at an AlI Center: Preparation of Terminally Bound Aluminum Sulfides
Type: info:eu-repo/semantics/article
Repository: DUGiDocs

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