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Abstract
Reaction of [(dppf)Au 2Br 2] ( 3) {dppf = 1,1′-bis(diphenylphosphino)ferrocene} and [(dippf)Au 2Br 2] ( 4) {dippf = 1,1′-bis(diisopropylphosphino)ferrocene} with excess bromine yields two new complexes [(C 5H 4Br 3)(PR 2)AuBr] (R = Ph, 5; R = i-Pr, 6). Bromination of the free diphosphinoferrocene ligands produces the expected brominated cyclopentenes (C 5H 4Br 3)(PR 2) (R = Ph, 7; R = i-Pr, 8) in good yields; however, these compounds could not be complexed to gold due to reduced basicity of 7 and 8. When the bromination is performed under wet aerobic conditions the oxidized pseudo-centrosymmetric product, [doppf][FeBr 4] ( 9) {doppf = 1,1′-bis(oxodiphenylphosphino)ferrocene, is formed as the major product. Solid-state structures of 1, 2, 4, 6, and 9 have been established by means of single-crystal X-ray crystallography.
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