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

Annie L. Colebatch; Alasdair I. McKay; Nicholas A. Beattie; Stuart A. Macgregor; Andrew S. Weller

doi:10.1002/ejic.201700600

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

Annie L. Colebatch, Alasdair I. McKay, Nicholas A. Beattie, Stuart A. Macgregor^*, Andrew S. Weller

^*Corresponding author for this work

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Abstract

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.

Original language	English
Pages (from-to)	4533-4540
Number of pages	8
Journal	European Journal of Inorganic Chemistry
Volume	2017
Issue number	38-39
Early online date	4 Aug 2017
DOIs	https://doi.org/10.1002/ejic.201700600
Publication status	Published - 25 Oct 2017

Keywords

Amines
Boranes
Fluoroarenes
Phosphines
Rhodium

ASJC Scopus subject areas

Inorganic Chemistry

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title = "Fluoroarene Complexes with Small Bite Angle Bisphosphines: Routes to Amine–Borane and Aminoborylene Complexes",

abstract = "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.",

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AU - Colebatch, Annie L.

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AU - Beattie, Nicholas A.

AU - Macgregor, Stuart A.

AU - Weller, Andrew S.

PY - 2017/10/25

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N2 - 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.

AB - 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.

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KW - Phosphines

KW - Rhodium

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

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