European Journal of Inorganic Chemistry
European Journal of Inorganic Chemistry
4 years ago

Fluoroarene Complexes with Small Bite Angle Bisphosphines: Routes to Amine–Borane and Aminoborylene Complexes

Fluoroarene Complexes with Small Bite Angle Bisphosphines: Routes to Amine–Borane and Aminoborylene Complexes
Andrew S. Weller, Stuart A. Macgregor, Nicholas A. Beattie, Alasdair I. McKay, Annie L. Colebatch
Fluoroarene complexes of the small bite angle bisphosphine Cy2PCH2PCy2 (dcpm) have been prepared: [Rh(dcpm)(η6-1,2-F2C6H4)][Al{OC(CF3)3}4] and [Rh(dcpm)(η6-1,2,3-F3C6H3)][Al{OC(CF3)3}4]. These complexes act as precursors to a previously inaccessible σ-amine–borane complex [Rh(dcpm)(η2-H3B·NMe3)][Al{OC(CF3)3}4] of a small bite-angle phosphine. This complex is a poor catalyst for the dehydrocoupling of H3B·NMe2H. Instead, formation of the bridging borylene complex [{RhH(µ-dcpm)}2(µ-H)(µ-BNMe2)][Al{OC(CF3)3}4] occurs, which has been studied by NMR, mass spectrometry, crystallographic and DFT techniques. This represents a new route to bridging borylene complexes.Synthesis of a Rh–trifluoroarene complex allows access to a bridging borylene complex by an amine–borane dehydrogenation/B–H activation.

Publisher URL: http://onlinelibrary.wiley.com/resolve/doi

DOI: 10.1002/ejic.201700600

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