Fluoroarene Complexes with Small Bite Angle Bisphosphines: Routes to Amine–Borane and Aminoborylene Complexes. Issue 38 (4th August 2017)

• Record Type: Journal Article
• Authors: Colebatch, Annie L.; McKay, Alasdair I.; Beattie, Nicholas A.; Macgregor, Stuart A.; Weller, Andrew S.
• Other Names: Bregadze Vladimir I. guestEditor.; Xie Zuowei guestEditor.
• Is Part Of: European journal of inorganic chemistry. Issue 38/39(2017)
• Page Start: 4533
• Page End: 4540
• Publication Date: 2017-08-04
• Subjects: Amines -- Rhodium -- Boranes -- Fluoroarenes -- Phosphines; Chemistry, Inorganic -- Periodicals; Organometallic chemistry -- Periodicals; Bioinorganic chemistry -- Periodicals; Solid state chemistry -- Periodicals; 546
• DOI: 10.1002/ejic.201700600
• Languages: English
• ISSNs: 1434-1948

Abstract

Abstract : Fluoroarene complexes of the small bite angle bisphosphine Cy2 PCH2 PCy2 (dcpm) have been prepared: [Rh(dcpm)(η 6 ‐1, 2‐F2 C6 H4 )][Al{OC(CF3 )3 }4 ] and [Rh(dcpm)(η 6 ‐1, 2, 3‐F3 C6 H3 )][Al{OC(CF3 )3 }4 ]. These complexes act as precursors to a previously inaccessible σ‐amine–borane complex [Rh(dcpm)(η 2 ‐H3 B· NMe3 )][Al{OC(CF3 )3 }4 ] of a small bite‐angle phosphine. This complex is a poor catalyst for the dehydrocoupling of H3 B· NMe2 H. 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. Abstract : Synthesis of a Rh–trifluoroarene complex allows access to a bridging borylene complex by an amine–borane dehydrogenation/B–H activation.