Nucleophilic addition of phosphines to rhenium allenylidenes. Unprecedented double P–H bond activation to give an η1-P-phospha-1-butadienyl ligand

Maurizio Peruzzini; Pierluigi Barbaro; Valerio Bertolasi; Claudio Bianchini; Isaac de los Rios; Nicoletta Mantovani; Lorenza Marvelli; Roberto Rossi

doi:10.1039/B303216G

Nucleophilic addition of phosphines to rhenium allenylidenes. Unprecedented double P–H bond activation to give an η¹-P-phospha-1-butadienyl ligand†

Maurizio Peruzzini,*^a Pierluigi Barbaro,^a Valerio Bertolasi,^b Claudio Bianchini,*^a Isaac de los Rios,^c Nicoletta Mantovani,^d Lorenza Marvelli*^d and Roberto Rossi^d

Author affiliations

* Corresponding authors

^a Istituto di Chimica dei Composti Organometallici (ICCOM-CNR), Via J. Nardi 39, 50132 Firenze, Italy
E-mail: bianchin@fi.cnr.it, peruz@fi.cnr.it

^b Centro di Strutturistica Diffrattometrica, Dipartimento di Chimica, Università di Ferrara, Via L. Borsari 46, 44100 Ferrara, Italy

^c Departamiento de Ciencia de los Materiales e Ing. Met. y Quimica Inorganica, Facultad de Ciencias, Universidad de Cadiz, Apartado 40, Puerto Real 11510, Spain

^d Laboratorio di Chimica Nucleare ed Inorganica, Dipartimento di Chimica, Università di Ferrara, Via L. Borsari 46, 44100 Ferrara, Italy
E-mail: mg1@dns.unife.it

Abstract

Tertiary phosphines PMe_3−xPh_x (x = 0–2) react with the rhenium allenylidene [(triphos)(CO)₂Re(C [double bond, length as m-dash] CCPh₂)]OTf (1) yielding γ-phosphonioalkynyl complexes [(triphos)(CO)₂Re{C [triple bond, length as m-dash] CCPh₂(PMe_3−xPh_x)}]OTf [x = 0, (2); 1, (4); 2 (7)] which convert into the α-phosphonioallenyl derivatives [(triphos)(CO)₂Re{C(PMe_3−xPh_x)CCPh₂}]OTf [x = 0, (3); 1, (5); 2 (6)] at higher tempereature. The reactions of 1 with secondary, PHPh₂, and primary, PH₂CH₂Fc (Fc = ferrocenyl), phosphines proceed with a similar mechanism, followed by single or double P–H bond cleavage. The γ-phosphonioalkynyl [(triphos)(CO)₂Re{C [triple bond, length as m-dash] CCPh₂(PHPh₂)}]OTf (9) and the α-phosphonioallenyl [(triphos)(CO)₂Re{C(PHPh₂) [double bond, length as m-dash] CCPh₂}]OTf (10) have been intercepted by insitu NMR spectroscopy. On increasing the temperature, 10 undergoes a selective 1,3-P,C-H shift to give the α-phosphoniobutadienyl derivative [(triphos)(CO)₂Re{C(PPh₂)CHCPh₂}]OTf (8). With the primary phosphine PH₂CH₂Fc, the initially formed α-phosphoniobutadienyl complex [(triphos)(CO)₂Re{C( [double bond, length as m-dash] PHFc)CHCPh₂}]OTf (11) transforms into the η¹-P-phospha-1-butadienyl complex [(triphos)(CO)₂Re{P(CH₂Fc)CHCHCPh₂}]OTf (12) upon heating at 50 °C.

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Article information

DOI: https://doi.org/10.1039/B303216G
Article type: Paper
Submitted: 24 Mar 2003
Accepted: 22 May 2003
First published: 22 Sep 2003

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Dalton Trans., 2003, 4121-4131

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Nucleophilic addition of phosphines to rhenium allenylidenes. Unprecedented double P–H bond activation to give an η¹-P-phospha-1-butadienyl ligand

M. Peruzzini, P. Barbaro, V. Bertolasi, C. Bianchini, I. D. L. Rios, N. Mantovani, L. Marvelli and R. Rossi, Dalton Trans., 2003, 4121 DOI: 10.1039/B303216G

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