Cyclo-oligomerisation reactions of bis(alkyne) and η2-vinyl complexes of molybdenum and tungsten with t-butyl isocyanide leading to iminocyclopentadiene derivatives
- 1 January 1988
- journal article
- Published by Royal Society of Chemistry (RSC) in J. Chem. Soc., Dalton Trans.
- No. 1,p. 27-34
- https://doi.org/10.1039/dt9880000027
Abstract
Reactions of t-butyl isocyanide with bis(alkyne) complexes [M(SR)(CF3CCCF3)2(η5-C5H5)](M = Mo, R = C6F5; M = W, R = C6H4Me-4) and isomeric η2-vinyl complexes [W{C(CF3)C(CF3)SR}(CF3CCCF3)(η5-C5H5)](R = Me, Pri, or But) give bis(isocyanide)-metallacyclic derivatives [[graphic omitted](CF3)}(SR)(CNBut)2(η5-C5H5)](7), viaη2-vinyl, [M{η2-C(CF3)C(CF3)CNBut}(SR)(CF3CCCF3)(η5-C5H5)](M = Mo, R = C6F5), or 16-electron monoisocyanide complexes, [[graphic omitted](CF3)}(SR)(CNBut)(η5-C5H5)](6), isolated for M = W, R = But. Metallacyclic complexes (6)(R = But) and (7)(M = W; R = C6H4Me-4, Pri, or But) can be hydrolysed to the iminoacyl oxo complex [W{η3-C(NBut)C(CF3)C(CF3)C(CF3)C(CF3)H}(O)(η5-C5H5)] whereas thermolysis of (7)(M = Mo, R = C6F5; M = W, R = Pri) gives complexes [M(SR)(CNBut){η2-C4(CF3)4CNBut}(η5-C5H5)] containing an iminocyclopentadiene ligand bonded in a novel η2 manner via the exocyclic C–N bond to the metal.Keywords
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