Hydrogen-Mediated Metal−Carbon to Metal−Boron Bond Conversion in Metal−Carboranyl Complexes
A hydrogen-mediated Ru−C to Ru−B bond conversion was observed experimentally and supported by the theoretical calculations. Treatment of [η5:σC-Me2C(C5H4)(C2B10H10)]Ru(COD) (1) bearing a Ru−C(cage) σ bond with PR3 in the presence of H2 gave Ru−B(cage) bonded complexes [η5:σB-Me2C(C5H4)(C2B10H10)]RuH...
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Veröffentlicht in: | Journal of the American Chemical Society 2008-11, Vol.130 (47), p.16103-16110 |
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Hauptverfasser: | , , , , , |
Format: | Artikel |
Sprache: | eng |
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Zusammenfassung: | A hydrogen-mediated Ru−C to Ru−B bond conversion was observed experimentally and supported by the theoretical calculations. Treatment of [η5:σC-Me2C(C5H4)(C2B10H10)]Ru(COD) (1) bearing a Ru−C(cage) σ bond with PR3 in the presence of H2 gave Ru−B(cage) bonded complexes [η5:σB-Me2C(C5H4)(C2B10H10)]RuH2(PR3) (R = Cy (2), Ph (3)) (σC: Ru−C(cage) σ bond; σB: Ru−B(cage) σ bond). Complex 3 was converted to [η5:σB-Me2C(C5H4)(C2B10H10)]Ru(L2) in the presence of L2 (L2 = dppe (4), PPh3/P(OEt)3 (5), PPh3/pyridine (6)) via liberation of H2 upon heating. These complexes were fully characterized by various spectroscopic techniques, elemental analyses, and single-crystal X-ray diffraction studies. DFT calculations show that this conversion process is both kinetically and thermodynamically favorable and requires involvement of a hydride ligand. |
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ISSN: | 0002-7863 1520-5126 |
DOI: | 10.1021/ja8067098 |