Issue 39, 2014

C–H bond activation and S-atom transfer from cobalt(iii) thiolate and isothiocyanate complexes

Abstract

The cobalt phenylthiolate complex, cis,mer-(PMe3)3Co(CH3)2SPh, was found to undergo competitive two-electron ethane reductive elimination and C–H bond cyclometallation. The thiophenolato bound cobaltacycle was generated via C–H bond oxidative addition to a five-coordinate intermediate followed by rapid methane elimination. A related cobalt isothiocyanate complex, cis,mer-(PMe3)3Co(CH3)2NCS, was also prepared and found to perform ethane elimination and S-atom transfer to yield trimethylphosphine sulfide. This rare example of S-atom donation from a isothiocyanate was characterized by NMR and GC-MS analysis, with cis,mer-(PMe3)3Co(CH3)2CN identified as one of the cobalt based products.

Graphical abstract: C–H bond activation and S-atom transfer from cobalt(iii) thiolate and isothiocyanate complexes

Supplementary files

Article information

Article type
Paper
Submitted
18 Jun 2014
Accepted
12 Aug 2014
First published
21 Aug 2014

Dalton Trans., 2014,43, 14696-14700

C–H bond activation and S-atom transfer from cobalt(III) thiolate and isothiocyanate complexes

H. Xu, P. G. Williard and W. H. Bernskoetter, Dalton Trans., 2014, 43, 14696 DOI: 10.1039/C4DT01823K

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