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DOI: 10.1039/A905892C (Paper) Reference Section for: J. Chem. Soc., Dalton Trans., 1999, 4325-4329

Oxidation of [M(η-C5H5)2], M = Cr, Fe or Co, by the new Brønsted acid H2O·B(C6F5)3 yielding the salts [M(η-C5H5)2]+A–, where A– = [(C6F5)3B(µ-OH)B(C6F5)3]– or [(C6F5)3BOH[hair space][hair space]· · ·[hair space][hair space]H2OB(C6F5)3]–[hair space]†

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Linda H. Doerrer and Malcolm L. H. Green

Abstract

The Brønsted acids H2O·B(C6F5)3 and D2O·B(C6F5)3 have been synthesized. Reaction of neutral divalent metallocenes [M(η-C5H5)2], M = Cr, Fe or Co, with two equivalents of H2O·B(C6F5)3 2a resulted in metallocene oxidation and formation of salts containing [M(η-C5H5)2]+ cations together with the hydroxoborate anion [HOB(C6F5)3]– which is hydrogen bonded to the second acid equivalent, namely [M(η-C5H5)2][(F5C6)3BOH[hair space][hair space]· · ·[hair space][hair space]H2OB(C6F5)3], M = Cr 3a, Fe 4a or Co 5a. Treatment of one equivalent of 2a and one equivalent of B(C6F5)3 1 with [M(η-C5H5)2] yielded salts containing the same metallocene cations but now with µ-OH bridged anions, as in [M(η-C5H5)2][(F5C6)3B(µ-OH)B(C6F5)3], where M = Cr 3b or Co 5b. All products have been characterised by NMR spectroscopy, elemental analysis, and the single-crystal structures of 2a, 3a, 4a, and 5a have been determined.

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