Trihydroborates and Dihydroboranes Bearing a Pentacoordinated Phosphorus Atom: Double Ring Expansion To Balance the Coordination States

Naokazu Kano; Nathan J O'Brien; Ryohei Uematsu; Romain Ramozzi; Keiji Morokuma

doi:10.1002/anie.201701718

Trihydroborates and Dihydroboranes Bearing a Pentacoordinated Phosphorus Atom: Double Ring Expansion To Balance the Coordination States

Angew Chem Int Ed Engl. 2017 May 15;56(21):5882-5885. doi: 10.1002/anie.201701718. Epub 2017 Apr 24.

Authors

Naokazu Kano¹, Nathan J O'Brien¹, Ryohei Uematsu², Romain Ramozzi², Keiji Morokuma²

Affiliations

¹ Department of Chemistry, Graduate School of Science, The University of Tokyo, 7-3-1 Hongo, Bunkyo-ku, Tokyo, 113-0033, Japan.
² Fukui Institute for Fundamental Chemistry, Kyoto University, Takano-Nishihiraki-cho 34-4, Sakyou-ku, Kyoto, 606-8103, Japan.

PMID: 28436088
DOI: 10.1002/anie.201701718

Abstract

The first trihydroborate bearing a pentacoordinated phosphorus atom was synthesized as a new P-B bonded compound. Hydride abstraction of the trihydroborate gave an intermediary dihydroborane, which showed hydroboration reactivity and was trapped with pyridine whilst maintaining the P-B bond. The dihydroborane underwent a rearrangement, which involved a double ring expansion to compensate for the unbalanced coordination states of the phosphorus and boron atoms, to give a new fused bicyclic phosphine-boronate.

Keywords: X-ray diffraction; boron; phosphorus; rearrangements; structure elucidation.

Publication types

Research Support, Non-U.S. Gov't