Abstract
Electron-rich metal carbene complexes, the 1,3-dithiol-2-ylidene iron(0) derivatives obtained in one step from Fe(CS2)(CO)2(PR3)2 and alkynes, can be stabilized by donor-acceptor Hg(II)→Fe(0) bond formation. Their protonation mechanism involves formation of the trans hydrido iron intermediate, isomerisation into the cis hydrido iron species, 1,2-hydrogen shift from the metal to the carbene carbon and coordination of one sulphur atom. The dimerisation of the carbene ligand into tetrathiafulvalene derivative is achieved either by thermolysis, oxidation with iodine or electrocatalysis. The interaction of RuCl2(PR3)(arene) complexes with terminal alkynes in the presence of alcohol provides a general route to arene-ruthenium-carbene complexes, via arene-ruthenium-vinylidene intermediates. RuCl2(PR3)(arene) complexes react with vinylacetylene to produce allylcarbene ruthenium derivative and with disubstituted propargyl alcohols to give, via an allenylidene intermediate, vinylcarbene-ruthenium complexes. The electronic RuCl2(PR3)(arene) and RuCl(PR3)2(C5H5) complexes have different oxidation potential and behave quite differently toward alkynes.
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dedicated to Prof. E.O. Fischer, on the occasion of his 70th birthday, for the creation of the metal-carbene complex chemistry.
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© 1989 Kluwer Academic Publishers
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Le Bozec, H., Devanne, D., Dixneuf, P.H. (1989). Metal Carbene Complexes from Alkynes. In: Schubert, U. (eds) Advances in Metal Carbene Chemistry. NATO ASI Series, vol 269. Springer, Dordrecht. https://doi.org/10.1007/978-94-009-2317-1_12
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