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Fluoroarene Complexes with Small Bite Angle Bisphosphines: Routes to Amine–Borane and Aminoborylene Complexes
Author(s) -
Colebatch Annie L.,
McKay Alasdair I.,
Beattie Nicholas A.,
Macgregor Stuart A.,
Weller Andrew S.
Publication year - 2017
Publication title -
european journal of inorganic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.667
H-Index - 136
eISSN - 1099-0682
pISSN - 1434-1948
DOI - 10.1002/ejic.201700600
Subject(s) - chemistry , borane , phosphine , amine gas treating , crystallography , catalysis , stereochemistry , medicinal chemistry , organic chemistry
Fluoroarene complexes of the small bite angle bisphosphine Cy 2 PCH 2 PCy 2 (dcpm) have been prepared: [Rh(dcpm)(η 6 ‐1,2‐F 2 C 6 H 4 )][Al{OC(CF 3 ) 3 } 4 ] and [Rh(dcpm)(η 6 ‐1,2,3‐F 3 C 6 H 3 )][Al{OC(CF 3 ) 3 } 4 ]. These complexes act as precursors to a previously inaccessible σ‐amine–borane complex [Rh(dcpm)(η 2 ‐H 3 B · NMe 3 )][Al{OC(CF 3 ) 3 } 4 ] of a small bite‐angle phosphine. This complex is a poor catalyst for the dehydrocoupling of H 3 B · NMe 2 H. Instead, formation of the bridging borylene complex [{RhH(µ‐dcpm)} 2 (µ‐H)(µ‐BNMe 2 )][Al{OC(CF 3 ) 3 } 4 ] occurs, which has been studied by NMR, mass spectrometry, crystallographic and DFT techniques. This represents a new route to bridging borylene complexes.