TY - JOUR
T1 - Heterolytic activation of hydrogen using frustrated Lewis pairs containing tris(2,2 ',2 ''-perfluorobiphenyl)borane
AU - Binding, Samantha C.
AU - Zaher, Hasna
AU - Mark Chadwick, F.
AU - O'Hare, Dermot
PY - 2012/8/14
Y1 - 2012/8/14
N2 - The extremely sterically hindered borane tris(2,2′,2″- perfluorobiphenyl)borane (PBB) has been structurally characterised. In combination with bulky nitrogen bases, it forms the 'frustrated Lewis pairs' (FLPs) PBB/2,2,6,6-tetramethylpiperidine (TMP) (1), PBB/1,4-diazobicyclo[2.2.2]- octane (DABCO) (2) and PBB/2,6-lutidine (lut) (3). These novel, unquenched acid-base pairs have been shown to effect facile room temperature heterolytic cleavage of dihydrogen to form the ammonium borate salts [2,2,6,6-Me 4C5H6NH2][HB(C12F 9)3] (4) and [N(C2H4) 3NH][HB(C12F9)3] (5), and lutidinium borate [2,6-Me2C5H3NH][HB(C12F 9)3] (6). Although these reactions are equilibria, the reverse reaction and release of hydrogen gas was not apparent at temperatures up to 120 °C. The relative Lewis acidity of PBB has been determined using the Gutmann-Beckett method.
AB - The extremely sterically hindered borane tris(2,2′,2″- perfluorobiphenyl)borane (PBB) has been structurally characterised. In combination with bulky nitrogen bases, it forms the 'frustrated Lewis pairs' (FLPs) PBB/2,2,6,6-tetramethylpiperidine (TMP) (1), PBB/1,4-diazobicyclo[2.2.2]- octane (DABCO) (2) and PBB/2,6-lutidine (lut) (3). These novel, unquenched acid-base pairs have been shown to effect facile room temperature heterolytic cleavage of dihydrogen to form the ammonium borate salts [2,2,6,6-Me 4C5H6NH2][HB(C12F 9)3] (4) and [N(C2H4) 3NH][HB(C12F9)3] (5), and lutidinium borate [2,6-Me2C5H3NH][HB(C12F 9)3] (6). Although these reactions are equilibria, the reverse reaction and release of hydrogen gas was not apparent at temperatures up to 120 °C. The relative Lewis acidity of PBB has been determined using the Gutmann-Beckett method.
UR - http://www.scopus.com/inward/record.url?scp=84863946683&partnerID=8YFLogxK
U2 - 10.1039/c2dt30334e
DO - 10.1039/c2dt30334e
M3 - Article
C2 - 22511223
AN - SCOPUS:84863946683
SN - 1477-9226
VL - 41
SP - 9061
EP - 9066
JO - Dalton Transactions
JF - Dalton Transactions
IS - 30
ER -