J. Podlaha, P. Štěpnička, Andrew Ludvik
Jan 23, 1996
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Organometallics
Abstract
The ferrocene derivative (η5-C5H4PPh2)Fe(η5-C5H4COOH) (3), a potential hybrid phosphine ligand with heteroannular soft and hard donor groups, was synthesized in 71% yield from 1-phenyl-1-phospha[1]ferrocenophane by ring opening with phenyllithium, followed by reaction with carbon dioxide and acidification. Oxidation of 3 with hydrogen peroxide and its esterification with diazomethane provided the derivatives, phosphine oxide 4 and methyl ester 5, respectively. The new compounds were characterized by IR, UV/vis, MS, and NMR spectroscopy, the degenerate 1H NMR spectra being assigned with the aid of selective 1H{1H} decoupling, 1H,1H-COSY, 13C HMQC, and nJ(P,C) from APT. The solid-state structures of 3−5 were determined by single-crystal X-ray diffraction. Voltammetric measurements of 3−5 and related monosubstituted derivatives in acetonitrile revealed that the phosphines are first oxidized to the corresponding ferrocenium derivatives which are then the subject of the intramolecular electron transfer from th...