2024-03-28T09:37:30Zhttp://digital.csic.es/dspace-oai/requestoai:digital.csic.es:10261/1113902016-02-18T02:59:19Zcom_10261_52707com_10261_5col_10261_52708
Reversible insertion of carbenes into ruthenium-silicon bonds
Bernal, María J.
Torres, Olga
Martín, Marta
Sola, Eduardo
Ministerio de Economía y Competitividad (España)
Consejo Superior de Investigaciones Científicas (España)
The five-coordinate carbene complexes [Ru{κP,P,Si-Si(Me)(C 6H4-2-PiPr2)2}Cl(=CHR)] (2, R = Ph; 3, R = SiMe3), analogues of the Grubbs catalyst, were prepared from the dimer [Ru(μ-Cl){κP,P,Si-Si(Me)(C6H4-2- PiPr2)2}]2 (1) and the corresponding diazoalkane N2CHR. The particular structural features that result from the presence of a strongly trans directing silyl group at the pincer ligand of these complexes are discussed on the basis of NMR information and the crystal structure of the vinylidene analogue [Ru{κP,P,Si-Si(Me)(C 6H4-2-PiPr2)2}Cl(=C=CHPh)] (4), which was also obtained from 1 and phenylacetylene. The reactions of 3 with reagents such as P(OMe)3, CO, NCMe, and K(acac) illustrate that the first response of these carbene complexes to an increase of the coordination number around ruthenium is the insertion of the carbene ligand into the Ru-Si bond. These reactions also indicate that the insertion process is reversible and allows typical transformations of carbene ligands such as C-H functionalizations via carbene insertion (in the acac ligand) or the formation of ketene from CO. In addition, the reactions of 3 with terminal alkynes such as phenylacetylene or 3,3-dimethyl-1-butyne show that the inserted carbenes can also undergo reactions typical of metal-bound alkyls such as alkyne insertion and C-H reductive elimination. © 2013 American Chemical Society.
This research was supported by the Spanish MINECO (Grants CTQ2009-08023 and CTQ2012-31774) and CSIC (Grant PIE 201280E109).
Peer Reviewed
2015-02-26T12:21:53Z
2015-02-26T12:21:53Z
2013
2015-02-26T12:21:53Z
artículo
http://purl.org/coar/resource_type/c_6501
doi: 10.1021/ja410822p
issn: 0002-7863
e-issn: 1520-5126
Journal of the American Chemical Society 135(50): 19008-19015 (2013)
http://hdl.handle.net/10261/111390
10.1021/ja410822p
http://dx.doi.org/10.13039/501100003329
http://dx.doi.org/10.13039/501100003339
Postprint
http://dx.doi.org/10.1021/ja410822p
Sí
open
American Chemical Society