Please use this identifier to cite or link to this item: http://hdl.handle.net/10261/19170
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Title

Influence of the Anion of the Salt Used on the Coordination Mode of an N-Heterocyclic Carbene Ligand to Osmium

AuthorsBaya, Miguel CSIC ORCID; Eguillor, Beatriz CSIC; Esteruelas, Miguel A. CSIC ORCID; Oliván, Montserrat ; Oñate, Enrique CSIC ORCID
Issue Date27-Nov-2007
PublisherAmerican Chemical Society
CitationOrganometallics 26(26): 6556-6563 (2007)
AbstractThe reactions of the hexahydride OsH6(PiPr3)2 (1) with 1.0 equiv of the BPh4−, BF4−, and Br− salts of 1-(2-pyridylmethyl)-3-methylimidazolium, in tetrahydrofuran under reflux, have been studied. In the three cases, mixtures of the abnormal [OsH(η2-H2){κC5,N-[1-(2-pyridylmethyl)-3-methylimidazol-5-ylidene]}(PiPr3)2]A (A = BPh4 (2a), BF4 (2b), Br (2c)) and normal [OsH(η2-H2){κC2,N-[1-(2-pyridylmethyl)-3-methylimidazol-2-ylidene]}(PiPr3)2]A (A = BPh4 (3a), BF4 (3b), Br (3c)) isomers are obtained. The formation rate of the abnormal isomer and the abnormal to normal ratio decrease as the coordinating power of the anion of the used salt increases. Treatment of 2b with either HBF4·OEt2 or LiBF4 gives rise to its isomerization to 3b. The X-ray structure of 2a and T1(min) values of the OsH3 resonances of the cations support the hydride-elongated dihydrogen nature of these compounds. The nonclassical interaction between the hydrogen atoms of the OsH3 unit is more important in the normal isomer than in the abnormal. Treatment of 1 with 2.0 equiv of 1-(2-pyridylmethyl)-3-methylimidazolium bromide yields the bis(normal-NHC) complex [OsH{κC2,N-[1-(2-pyridylmethyl)-3-methylimidazol-2-ylidene]}2(PiPr3)]Br (4), which has been also characterized by X-ray diffraction analysis.
Description8 pages, 6 figures, 1 table.
Publisher version (URL)http://dx.doi.org/10.1021/om700746h
URIhttp://hdl.handle.net/10261/19170
DOI10.1021/om700746h
ISSN0276-7333
Appears in Collections:(ICMA) Artículos

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