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First Examples of Rhenium-Assisted Activation of Propargyl Alcohols:  Allenylidene, Carbene, and Vinylidene Rhenium(I) Complexes

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Laboratorio di Chimica Nucleare ed Inorganica, Dipartimento di Chimica, Università di Ferrara, Via L. Borsari 46, 44100 Ferrara, Italy, Istituto per lo Studio della Stereochimica ed Energetica dei Composti di Coordinazione, CNR, Via J. Nardi 39, 50132 Firenze, Italy, and Departamento de Quimica Inorganica, Universidad de Almeria, 04071 Almeria, Spain
Cite this: Organometallics 1999, 18, 22, 4501–4508
Publication Date (Web):September 28, 1999
https://doi.org/10.1021/om990375x
Copyright © 1999 American Chemical Society

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    Abstract

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    The complex [(triphos)(CO)2Re(OTf)] (1) reacts with disubstituted propargyl alcohols HC⋮CCR(R‘)OH in CH2Cl2 at room temperature (R = R‘ = Ph, Me; R = Ph, R‘ = Me), to give either allenylidene derivatives [(triphos)(CO)2Re{CCC(R)Ph}]OTf (R = Ph, 2; R = Me, 3) or the dinuclear vinylidene−carbene complex [{(triphos)(CO)2Re}2{μ-(C10H12)}](OTf)2 (5) (R = R‘ = Me) (triphos = MeC(CH2PPh2)3; OTf = CF3SO3-). The secondary propargyl alcohol HC⋮CCH(Me)OH reacts with 1 in the presence of methanol to give the methoxyalkenyl Fischer-type carbene [(triphos)(CO)2Re{C(OMe)-CHCHMe}]OTf (11). Compound 11 has been authenticated by an X-ray diffraction analysis. The structure of this complex shows the metal center to be surrounded by a fac triphos ligand, by two mutually cis carbonyl groups, and by the organyl ligand in a slightly distorted octahedral geometry. The reaction with HC⋮CCH2OH results in the double addition of methanol to give the carbene complex [(triphos)(CO)2Re{C(OMe)(CH2CH2OMe)}]OTf (9). When the reaction between 1 and propargyl alcohol is carried out in the dichloromethane dinuclear vinylidene−carbene complex, [{(triphos)(CO)2Re}2{μ-(C6H6O)}](OTf)2 (10) is obtained.

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     Corresponding authors. E-mail:  [email protected]; [email protected]; [email protected].

     ISSECC CNR.

    §

     University of Ferrara.

     University of Almeria.

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    Tables of crystallographic data for 11. This material is available free of charge via the Internet at http://pubs.acs.org.

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