Issue 16, 2001
From the journal:

Journal of the Chemical Society, Dalton Transactions

Backward synthesis of rhenium(I) γ-hydroxyvinylidene and γ-methoxyvinylidene complexes and their conversion to the allenylidene [Re{C[double bond, length as m-dash]C[double bond, length as m-dash]CPh2}(CO)2(MeC(CH2PPh2)3)](OSO2CF3)

Nicoletta Mantovani,a   Lorenza Marvelli,a   Roberto Rossi,*a   Claudio Bianchini,*b   Isaac de los Rios,b   Antonio Romerosac  and  Maurizio Peruzzini*b  

* Corresponding authors

a Laboratorio di Chimica Nucleare ed Inorganica, Dipartimento di Chimica, Università di Ferrara, Via L. Borsari 46, 44100 Ferrara, Italy
E-mail: mg2@dns.unife.it

b Istituto per lo Studio della Stereochimica ed Energetica dei Composti di Coordinazione, CNR, Via J. Nardi 39, Firenze, Italy
E-mail: bianchin@fi.cnr.it; peruz@fi.cnr.it

c Área de Química Inorgánica, Facultad de Ciencias, Universidad de Almería, Almería, Spain

Abstract

The reactivity of the rhenium(I) allenylidene complex [Re{C[double bond, length as m-dash]C[double bond, length as m-dash]CPh2}(CO)2(triphos)](OTf) (1) [triphos = MeC(CH2PPh2)3] towards ionic nucleophiles and electrophiles has been explored. Nucleophiles regioselectively attack the Cγ carbon atom leading to the formation of σ-alkynyl complexes, while electrophiles attack the Cβ atom yielding carbyne complexes. The sequential addition of OH− and H+ to 1 at low temperature gave the γ-hydroxyvinylidene complex [Re{C[double bond, length as m-dash]C(H)C(OH)Ph2}(CO)2(triphos)](OTf) which regenerated 1 above −40 °C via H2O elimination.

Graphical abstract: Backward synthesis of rhenium(I) γ-hydroxyvinylidene and γ-methoxyvinylidene complexes and their conversion to the allenylidene [Re{C [[double bond, length as m-dash]] C [[double bond, length as m-dash]] CPh2}(CO)2(MeC(CH2PPh2)3)](OSO2CF3)

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Article information

DOI
https://doi.org/10.1039/B103293N
Article type
Paper
Submitted
12 Apr 2001
Accepted
05 Jun 2001
First published
30 Jul 2001

J. Chem. Soc., Dalton Trans., 2001, 2353-2361

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Backward synthesis of rhenium(I) γ-hydroxyvinylidene and γ-methoxyvinylidene complexes and their conversion to the allenylidene [Re{C[double bond, length as m-dash]C[double bond, length as m-dash]CPh2}(CO)2(MeC(CH2PPh2)3)](OSO2CF3)

N. Mantovani, L. Marvelli, R. Rossi, C. Bianchini, I. D. L. Rios, A. Romerosa and M. Peruzzini, J. Chem. Soc., Dalton Trans., 2001, 2353 DOI: 10.1039/B103293N

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