Selective displacement of chloride from
cyclopentadienyl(1,4-dichlorobenzene)iron(1+) by a
series
of cyclic secondary amine nucleophiles is described. This
selectivity, in combination with further
manipulation of the complexes, allows access to a series of
unsymmetrical and/or functionalized
tetraalkyl-p-phenylenediamine complexes. A series of
demetalated phenylenediamines were shown
by CV to have redox potentials distributed over a range of 320 mV, as a
consequence of remote
functionality. Preliminary fluorescence studies on a series of
electron acceptor-substituted
phenylenediamines indicated quenching of the phenylenediamine
fluorescence, attributable to rapid
electron transfer.
Demetalation of
dicarbonyl(π-allyl)[hydridotris(pyrazolyl)borato]molybdenum complexes can
be
achieved via lactonization. A carboxylic acid moiety
is
installed via addition of methyl phenylsulfonylacetate
enolate to a diene−Mo(CO)2Tp complex, followed
by
desulfonylation and hydrolysis, so that the subsequent
lactonization can be effected by CO/NO+ exchange
or
with iodine to give decomplexed products from cyclic and
acyclic complexes.
[Structure: see text] The conjugate additions of different carbon nucleophiles to cyclopentadienone substrates (1 and 2) with one free hydroxyl functional group were investigated to determine the role of the hydroxyl group in controlling regiochemistry. During this reaction an unexpected intramolecular displacement of OTBS by the enolate intermediate occurs, to afford cyclopropane derivatives.
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