Hydrogen-Mediated Metal−Carbon to Metal−Boron Bond Conversion in Metal−Carboranyl Complexes
- 31 October 2008
- journal article
- Published by American Chemical Society (ACS) in Journal of the American Chemical Society
- Vol. 130 (47), 16103-16110
- https://doi.org/10.1021/ja8067098
Abstract
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.Keywords
This publication has 83 references indexed in Scilit:
- Ruthenium-Catalyzed Homo and Cross Metathesis Reactions of Alkenylpolyboranes: New Routes to Functional o-Carborane and Decaborane DerivativesOrganometallics, 2005
- Facile and Mild Deboronation ofo-Carboranes Using Cesium FluorideInorganic Chemistry, 2001
- Mixed Cobaltacarboranes Incorporating η5-Pyrrolyl and Dicarbollide Ligands. Synthetic Routes, Structures, and Mechanistic ImplicationsOrganometallics, 1997
- Kernresonanzspektroskopische Untersuchungen an Borverbindungen, XIV. Indirekte Kern‐Spin‐Spin‐Kopplungen zwischen 11B und direkt borgebundenen KernenEuropean Journal of Inorganic Chemistry, 1977
- Nonicosahedral carboranes. Synthesis and reactionsAccounts of Chemical Research, 1973
- Kernresonanzuntersuchungen an Bor‐Verbindungen, I. 11B‐Kernresonanzspektren von Boranen mit Substituenten aus der ersten Achterperiode des PeriodensystemsEuropean Journal of Inorganic Chemistry, 1966
- Comments on the Reaction of Amines with 1,2-Dicarbaclovododecaborane(12)Inorganic Chemistry, 1965
- o-Carboranyl Derivatives of Boron CompoundsInorganic Chemistry, 1965
- Dicarbaundecaborane(13) and DerivativesJournal of the American Chemical Society, 1964
- A New Series of Organoboranes. III. Some Reactions of 1,2-Dicarbaclovododecaborane(12) and its DerivativesInorganic Chemistry, 1963