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Synthesis of Heterocyclic Ligands by Diheterocyclization at the Rhenium(I) Allenylidene [(triphos)(CO)2Re{CCCPh2}](OSO2CF3). 1. Reactivity with Dipolar N,N-Heterocycles

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Laboratorio di Chimica Nucleare ed Inorganica and Centro di Strutturistica Diffrattometrica, Dipartimento di Chimica, Università di Ferrara, Via L. Borsari 46, 44100 Ferrara, Italy, Istituto di Chimica dei Composti Organo Metallici, ICCOM CNR, Via Madonna del Piano 10, Area di Ricerca del CNR, 50019, Sesto Fiorentino, Italy, and Departamento Quimica Inorganica, Facultad de Ciencias, Campus Rio San Pedro, University of Cadiz, 11500 Puerto Real (Cadiz), Spain
Cite this: Organometallics 2006, 25, 2, 416–426
Publication Date (Web):December 9, 2005
https://doi.org/10.1021/om050663v
Copyright © 2006 American Chemical Society
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Abstract

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1,2,3-Diheterocyclizations at the allenylidene ligand in the complex [(triphos)(CO)2Re{CCCPh2}]OTf (1; triphos = MeC(CH2PPh2)3, OTf = OSO2CF3) readily occur upon reacting 1 with N,N-heterocycles such as 1H-benzotriazole, 2-aminopyridine, and 2-aminothiazole. The reaction of 1 with 1H-benzotriazole leads to (4). Deprotonation of 4 with sodium methoxide in tetrahydrofuran at room temperature yields the alkynyl derivative (5) via ring opening of the triazaindenyl moiety in 4. Reaction of 1 with 2-aminopyridine or 2-aminothiazole in CH2Cl2 leads to the heterobicyclic compounds (6) and (8), respectively. Both complexes undergo regioselective deprotonation at the N−H heterocycle group by treatment with sodium methoxide in THF, giving the neutral species (7) and (9), respectively. The X-ray structures of the new organorhenium species 4 and 79 have been determined, which have confirmed that the addition of the NH bond of the N,N-heterocycle occurs always across the Cβ−Cγ double bond of the allenylidene chain.

 Laboratorio di Chimica Nucleare ed Inorganica, Dipartimento di Chimica, Università di Ferrara.

*

In papers with more than one author, the asterisk indicates the name of the author to whom inquiries about the paper should be addressed.

 Centro di Strutturistica Diffrattometrica, Dipartimento di Chimica, Università di Ferrara.

 University of Cadiz.

§

 ICCOM CNR.

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  19. Cecilia Coletti, Nazzareno Re. Performance of DFT and MP2 Approaches for Geometry of Rhenium Allenylidenes Complexes and the Thermodynamics of Phosphines Addition. 2012,,, 738-751. https://doi.org/10.1007/978-3-642-31125-3_55
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