Heterolytic activation of hydrogen using frustrated Lewis pairs containing tris(2,2',2'-perfluorobiphenyl)borane |
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Authors: | Binding Samantha C Zaher Hasna Mark Chadwick F O'Hare Dermot |
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Institution: | Inorganic Chemistry Laboratory, University of Oxford, South Parks Road, Oxford, OX1 3QR. |
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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-diazobicyclo2.2.2]-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(4)C(5)H(6)NH(2)]HB(C(12)F(9))(3)] (4) and N(C(2)H(4))(3)NH]HB(C(12)F(9))(3)] (5), and lutidinium borate 2,6-Me(2)C(5)H(3)NH]HB(C(12)F(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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