Heterolytic activation of hydrogen using frustrated Lewis pairs containing tris(2,2 ',2 ''-perfluorobiphenyl)borane

Samantha C. Binding; Hasna Zaher; F. Mark Chadwick; Dermot O'Hare

doi:10.1039/c2dt30334e

Heterolytic activation of hydrogen using frustrated Lewis pairs containing tris(2,2 ',2 ''-perfluorobiphenyl)borane

Samantha C. Binding, Hasna Zaher, F. Mark Chadwick, Dermot O'Hare^*

^*Corresponding author for this work

Research output: Contribution to journal › Article › peer-review

33 Citations (Scopus)

Abstract

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.

Original language	English
Pages (from-to)	9061-9066
Number of pages	6
Journal	Dalton Transactions
Volume	41
Issue number	30
DOIs	https://doi.org/10.1039/c2dt30334e
Publication status	Published - 14 Aug 2012

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title = "Heterolytic activation of hydrogen using frustrated Lewis pairs containing tris(2,2 ',2 ''-perfluorobiphenyl)borane",

abstract = "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.",

author = "Binding, \{Samantha C.\} and Hasna Zaher and \{Mark Chadwick\}, F. and Dermot O'Hare",

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AU - Zaher, Hasna

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AU - O'Hare, Dermot

PY - 2012/8/14

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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.

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DO - 10.1039/c2dt30334e

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AN - SCOPUS:84863946683

SN - 1477-9226

VL - 41

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EP - 9066

JO - Dalton Transactions

JF - Dalton Transactions

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ER -

Heterolytic activation of hydrogen using frustrated Lewis pairs containing tris(2,2 ',2 ''-perfluorobiphenyl)borane

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