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Issue 9, 1992
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Ethoxycarbonyl-, cyano- and methoxy-methyl complexes of nickel(II) and their carbonylation reactions

Abstract

The oxidative addition of ClCH2CO2Et, ClCH2CN and BrCH2OMe to [Ni(cod)2](cod = cycloocta-1,5-diene), in the presence of 2 equivalents of PMe3, affords the β-functionalized nickel(II) methyl derivatives trans-[Ni(CH2R)X(PMe3)2](R = CO2Et, X = Cl 1; R = CN, X = Cl 2; R = OMe, X = Br 3). The interaction of these complexes with carbon monoxide has been studied. The methoxymethyl derivative 3 forms a stable acyl of composition trans-[Ni{C(O)CH2OMe}Br(PMe3)2]7, but for the ethoxycarbonylmethyl complex 1 the corresponding acyl 8 forms reversibly and, although stable as a solid, only exists in solution under an atmosphere of carbon monoxide. No stable acyl has been observed from the reaction of 2 with CO; only decomposition occurs. Stable 18-electron alkyl and acyl cyclopentadienyl derivatives of composition [Ni(CH2R)(η-C5H5)(PMe3)](R = CO2Et 4; CN 5, or OMe 6) and [Ni{C(O)CH2R}(η-C5H5)(PMe3)](R = OMe 9 or CO2Et 10) are easily obtained upon reaction of the above 16-electron complexes with Na(C5H5). The new compounds have been fully characterized by analytical and spectroscopic (IR and 1H, 13C and 31P NMR) methods.

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Article information


J. Chem. Soc., Dalton Trans., 1992, 1491-1495
Article type
Paper

Ethoxycarbonyl-, cyano- and methoxy-methyl complexes of nickel(II) and their carbonylation reactions

T. R. Belderraín, D. A. Knight, D. J. Irvine, M. Paneque, M. L. Poveda and E. Carmona, J. Chem. Soc., Dalton Trans., 1992, 1491
DOI: 10.1039/DT9920001491

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