Nuclear Magnetic Resonance and Electronic Spectral Studies on the Formation of ?-Olefin-Tetracyanocobaltate(I) Complexes

DOI: 10.1039/DT9810002529

Source and publish data:

Journal of the Chemical Society, Dalton Transactions p. 2529 - 2536 (1981)

Update date:2022-08-05

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Authors:

Funabiki, Takuzo

Yoshida, Satohiro

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Article abstract of DOI:10.1039/DT9810002529

Cyanocobaltate prepared at CN:Co <5:1 in water in the presence of alkali and under an atmosphere of hydrogen reacts readily with mono-olefins having electron-withdrawing substituents to give a dark red solution.Hydrogen-1 and 13C n.m.r. spectra of the solutions in D2O clearly indicate that ?-olefin complexes of cyanocobaltate are formed.The solutions also exhibit characteristic bands near 450 nm.The stoicheiometry of complex formation has been studied using PhCH=C(CN)2 and monitored by the absorbance of the complex at 440 nm.These results indicate that a new type of ?-olefin-cobalt(I) complex, (3-), is formed, where olefin is (NC)2C=C(CN)2, PhCH=C(CN)2, cis- and trans-PhCH=CHCN, E-PhCH=C(CN)CO2Et, E-PhCH=C(CN)CO2K, or cis- and trans-RO2CCH=CHCO2R (R=Me, Et, or Na).The ? complex of dialkyl maleate isomerises to that of dialkyl fumarate, probably by an electron-transfer mechanism.

Full text of DOI:10.1039/DT9810002529

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