Abstract

To get further insight in the reaction of nucleophilic substitution upon changing the ligand trans to a eta(2)-olefin, the reactivity of some monoanionic platinum(II) complexes (trans-[PtCl2X(eta(2)-C2H4)](-), X = Cl-, 1, OH-, 2, and CH2NO2-, 3) towards pyridines with different steric hindrance (py, 4-Mepy, and 2,6-Me(2)py) has been tested. All crystallographic (2 and 3 reported for the first time) and spectroscopic data are in accord with a platinum-olefin interaction decreasing in the order 2 > 1 > 3, paralleling the decreasing electronegativity of the donor atom (O > Cl > C). Not only the platinum-olefin bond but also the bond between platinum and the ligand trans to the olefin appear to be strongest in 2 (Pt-O distance at the lower limit for this type of bond). In the reaction with py, the ligand trans to the olefin is displaced in 1 and 2. Moreover the reaction is in equilibrium in the case of sterically hindered 2,6-Me2py, the equilibrium being shifted moderately or prevalently toward the reagents in the case of 1 and 2, respectively. In the case of 3, the reaction with pyridines leads to substitution of the olefin instead of the carbanion. This is in accord with the observation that carbanions strongly weaken the trans Pt-olefin bond.

Autore Pugliese

• Fanizzi Francesco Paolo , Benedetti Michele

Tutti gli autori

• M. Benedetti , C. R. Barone , D. Antonucci , V. M. Vecchio , A. Ienco , L. Maresca , G. Natile , F. P. Fanizzi

Titolo volume/Rivista

DALTON TRANSACTIONS

Anno di pubblicazione

2012

ISSN

1477-9226

ISBN

Non Disponibile

Numero di citazioni Wos

21

Ultimo Aggiornamento Citazioni

28/04/2018

Numero di citazioni Scopus

20

Ultimo Aggiornamento Citazioni

28/04/2018

Settori ERC

Non Disponibile

Codici ASJC

Non Disponibile