Hydrogen-Mediated Metal−Carbon to Metal−Boron Bond Conversion in Metal−Carboranyl Complexes

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
Hauptverfasser: Liu, Dongmei, Dang, Li, Sun, Yi, Chan, Hoi-Shan, Lin, Zhenyang, Xie, Zuowei
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container_end_page 16110
container_issue 47
container_start_page 16103
container_title Journal of the American Chemical Society
container_volume 130
creator Liu, Dongmei
Dang, Li
Sun, Yi
Chan, Hoi-Shan
Lin, Zhenyang
Xie, Zuowei
description 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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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. 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Am. Chem. Soc</addtitle><date>2008-11-26</date><risdate>2008</risdate><volume>130</volume><issue>47</issue><spage>16103</spage><epage>16110</epage><pages>16103-16110</pages><issn>0002-7863</issn><eissn>1520-5126</eissn><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.</abstract><cop>United States</cop><pub>American Chemical Society</pub><pmid>18975873</pmid><doi>10.1021/ja8067098</doi><tpages>8</tpages></addata></record>
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