title: Dehydrogenative B-H/C(sp3)-H Benzylic Borylation within the Coordination Sphere of Platinum(II).
abstract: The first examples of stoichiometric dehydrogenative B-H/C(sp3)-H benzylic borylation reactions, which are of relevance to catalytic methylarene (di)borylation, are reported. These unusual transformations involving a (κ2-P,N)Pt(η3-benzyl) complex, and either pinacolborane or catecholborane, proceed cleanly at room temperature. Density functional calculations suggest that borylation occurs via successive σ-bond metathesis steps, whereby a PtII-H intermediate engages in C(sp3)-H bond activation-induced dehydrogenation.
authors.affiliation: Department of Chemistry, Dalhousie University, Halifax, Nova Scotia, B3H 4R2, Canada.
authors.forename: Colin M
authors.initials: CM
authors.lastname: Kelly
authors.affiliation: Department of Chemistry and Biochemistry, Brigham Young University, Provo, UT, 84602, USA.
authors.forename: Jack T
authors.initials: JT
authors.lastname: Fuller
authors.affiliation: Department of Chemistry, Dalhousie University, Halifax, Nova Scotia, B3H 4R2, Canada.
authors.forename: Casper M
authors.initials: CM
authors.lastname: Macaulay
authors.affiliation: X-ray Crystallography Laboratory, Department of Chemistry University of Alberta, Edmonton, Alberta, T6G 2G2, Canada.
authors.forename: Robert
authors.initials: R
authors.lastname: McDonald
authors.affiliation: X-ray Crystallography Laboratory, Department of Chemistry University of Alberta, Edmonton, Alberta, T6G 2G2, Canada.
authors.forename: Michael J
authors.initials: MJ
authors.lastname: Ferguson
authors.affiliation: Research and Technology, Chevron Phillips Chemical Company LP, 1862 Kingwood Drive, Kingwood, TX, 77339, USA.
authors.forename: Steven M
authors.initials: SM
authors.lastname: Bischof
authors.affiliation: Research and Technology, Chevron Phillips Chemical Company LP, 1862 Kingwood Drive, Kingwood, TX, 77339, USA.
authors.forename: Orson L
authors.initials: OL
authors.lastname: Sydora
authors.affiliation: Department of Chemistry and Biochemistry, Brigham Young University, Provo, UT, 84602, USA.
authors.forename: Daniel H
authors.initials: DH
authors.lastname: Ess
authors.affiliation: Department of Chemistry, Dalhousie University, Halifax, Nova Scotia, B3H 4R2, Canada.
authors.forename: Mark
authors.identifier: 0000-0002-6913-5160
authors.initials: M
authors.lastname: Stradiotto
authors.affiliation: Department of Chemistry, Dalhousie University, Halifax, Nova Scotia, B3H 4R2, Canada.
authors.forename: Laura
authors.initials: L
authors.lastname: Turculet
keywords: C−H borylation; DFT calculations; coordination chemistry; platinum