The sequence of fundamental steps implicit in the conversion of a dihydroborane to a metal borylene complex have been elucidated for an [Ir(PMe(3))(3)] system. B-H oxidative addition has been applied for the first time to an aminodihydroborane, H(2)BNR(2), leading to the generation of a rare example of a primary boryl complex, L(n)(H)M{B(H)NR(2)}; subsequent conversion to a borylene dihydride proceeds via a novel B-to-M α-hydride migration. The latter step is unprecedented for group 13 ligand systems, and is remarkable in offering α- substituent migration from a Lewis acidic center as a route to a two-coordinate ligand system.
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Transition-metal-carbene-like intermolecular insertion of a borylene into C-H bonds.
Chem Commun (Camb)
July 2020
Institute for Inorganic Chemistry, Julius-Maximilians-Universität Würzburg, Am Hubland, 97074 Würzburg, Germany. and Institute for Sustainable Chemistry & Catalysis with Boron, Julius-Maximilians-Universität Würzburg, Am Hubland, 97074 Würzburg, Germany.
We demonstrate that, in analogy to transition-metal carbene chemistry, [(OC)5Mo[double bond, length as m-dash]BN(SiMe3)2] facilitates intermolecular transfer of the borylene [:BN(SiMe3)2], which ultimately undergoes insertion into C-H bonds under very mild conditions. The one-pot multiple functionalization of the cyclopentadienyl rings of tungstenocene dihydride is demonstrated using this approach.
View Article and Find Full Text PDFBorane to boryl hydride to borylene dihydride: explicit demonstration of boron-to-metal α-hydride migration in aminoborane activation.
J Am Chem Soc
August 2011
Inorganic Chemistry Laboratory, Department of Chemistry, University of Oxford, South Parks Road, Oxford OX1 3QR, United Kingdom.
The sequence of fundamental steps implicit in the conversion of a dihydroborane to a metal borylene complex have been elucidated for an [Ir(PMe(3))(3)] system. B-H oxidative addition has been applied for the first time to an aminodihydroborane, H(2)BNR(2), leading to the generation of a rare example of a primary boryl complex, L(n)(H)M{B(H)NR(2)}; subsequent conversion to a borylene dihydride proceeds via a novel B-to-M α-hydride migration. The latter step is unprecedented for group 13 ligand systems, and is remarkable in offering α- substituent migration from a Lewis acidic center as a route to a two-coordinate ligand system.
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