title: Cobalt Boryl Complexes: Enabling and Exploiting Migratory Insertion in Base-Metal-Mediated Borylation.
abstract: Cobalt boryl complexes, which have only been sporadically reported, can be accessed systematically with remarkable (but controllable) variation in the nature of the M-B bond. Complexes incorporating a very strong trans σ-donor display unparalleled inertness, reflected in retention of the M-B bond even in the presence of extremely strong acid. By contrast, the use of the strong π-acceptor CO in the trans position, results in significant Co-B elongation and to labilization of the boryl ligand via unprecedented CO migratory insertion. Such chemistry provides a pathway for the generation of coordinative unsaturation, thereby enabling ligand substitution and/or substrate assimilation. Alkene functionalization by boryl transfer, a well-known reaction for noble metals such as Rh or Pt, can thus be effected by an 18-electron base-metal complex.
authors.affiliation: Inorganic Chemistry Laboratory, Department of Chemistry, University of Oxford, South Parks Road, Oxford OX1 3QR (UK).
authors.forename: René
authors.initials: R
authors.lastname: Frank
authors.affiliation: Inorganic Chemistry Laboratory, Department of Chemistry, University of Oxford, South Parks Road, Oxford OX1 3QR (UK).
authors.forename: James
authors.initials: J
authors.lastname: Howell
authors.affiliation: Inorganic Chemistry Laboratory, Department of Chemistry, University of Oxford, South Parks Road, Oxford OX1 3QR (UK).
authors.forename: Jésus
authors.initials: J
authors.lastname: Campos
authors.affiliation: Inorganic Chemistry Laboratory, Department of Chemistry, University of Oxford, South Parks Road, Oxford OX1 3QR (UK).
authors.forename: Rémi
authors.initials: R
authors.lastname: Tirfoin
authors.affiliation: Inorganic Chemistry Laboratory, Department of Chemistry, University of Oxford, South Parks Road, Oxford OX1 3QR (UK).
authors.forename: Nicholas
authors.initials: N
authors.lastname: Phillips
authors.affiliation: Fakultät für Chemie und Mineralogie, Wilhelm Ostwald Institut für Physikalische und Theoretische Chemie, Universität Leipzig, Linnéstrasse 2, 04103 Leipzig (Germany).
authors.forename: Stefan
authors.initials: S
authors.lastname: Zahn
authors.affiliation: Inorganic Chemistry Laboratory, Department of Chemistry, University of Oxford, South Parks Road, Oxford OX1 3QR (UK). michael.mingos@seh.ox.ac.uk.
authors.forename: D Michael P
authors.initials: DM
authors.lastname: Mingos
authors.affiliation: Inorganic Chemistry Laboratory, Department of Chemistry, University of Oxford, South Parks Road, Oxford OX1 3QR (UK). Simon.Aldridge@chem.ox.ac.uk.
authors.forename: Simon
authors.initials: S
authors.lastname: Aldridge
keywords: boron; boryl ligands; carbonyl ligands; cobalt; insertion reactions