2024-03-28T18:57:22Zhttp://digital.csic.es/dspace-oai/requestoai:digital.csic.es:10261/1111362016-02-18T03:06:49Zcom_10261_52707com_10261_5col_10261_52708
Cationic dihydride boryl and dihydride silyl osmium(IV) NHC complexes: A marked diagonal relationship
Buil, María L.
Esteruelas, Miguel A.
Fernández, Israel
Izquierdo, Susana
Oñate, Enrique
Ministerio de Economía y Competitividad (España)
Diputación General de Aragón
European Commission
Comunidad de Madrid
The complex [OsCl(η6-p-cymene)(IPr)]OTf (1; IPr = 1,3-bis(2,6-diisopropylphenyl)imidazolylidene, OTf = trifluoromethanesulfonate) reacts with pinacolborane (HBpin) and catecholborane (HBcat) to give the dihydride boryl osmium(IV) derivatives [OsH2(Bpin)(η6- p-cymene)(IPr)]OTf (2) and [OsH2(Bcat)(η6-p-cymene) (IPr)]OTf (3), which undergo hydrolysis to afford the trihydride [OsH 3(η6-p-cymene)(IPr)]OTf (4). In agreement with the boron-silicon diagonal relationship, complex 1 also reacts with silanes, HSiR3. The reactions lead to the dihydride silyl species [OsH 2(SiR3)(η6-p-cymene)(IPr)]OTf (SiR 3 = SiPh3 (5), SiEt3 (6), SiHPh2 (7)), which also undergo hydrolysis to yield 4. Complexes 2 and 5 have been characterized by X-ray diffraction analysis. Their four-legged piano-stool geometries with transoid hydride ligands are similar. In solution, the arene rotates over the remaining four ligands. The activation barrier of the process depends upon the size of the boryl or silyl groups. The nature of the Os-B and Os-Si interactions has been investigated by means of computational methods. Both of them are σ bonds with small or negligible π back-donation from the metal to the ligands. © 2013 American Chemical Society.
Financial support from the Spanish MINECO (Projects CTQ2011-23459 and Consolider Ingenio 2010 (CSD2007-00006)), the DGA (E35), and the European Social Fund (FSE) is acknowledged. I.F. thanks the Spanish MINECO and CAM (Grants CTQ2010-20714-CO2-01/BQU, S2009/PPQ-1634).
Peer Reviewed
2015-02-24T11:38:20Z
2015-02-24T11:38:20Z
2013
2015-02-24T11:38:20Z
artículo
http://purl.org/coar/resource_type/c_6501
doi: 10.1021/om400188z
issn: 0276-7333
e-issn: 1520-6041
Organometallics 32(9): 2744-2752 (2013)
http://hdl.handle.net/10261/111136
10.1021/om400188z
http://dx.doi.org/10.13039/501100003329
http://dx.doi.org/10.13039/501100000780
http://dx.doi.org/10.13039/100012818
#PLACEHOLDER_PARENT_METADATA_VALUE#
S2009/PPQ-1634/AVANCAT
none
American Chemical Society