Issue 1, 2013

Reactivity of 2-chalcogenopyridines with palladium–phosphine complexes: isolation of different complexes depending on the nature of chalcogen atom and phosphine ligand

Abstract

Reactions of either Pd(0) phosphine complexes with dipyridyldichalcogenides or [PdCl2(PP)] (PP = dppe, dppp) with pyridylchalcogenolate ions have been examined and a variety of Pd(II) complexes have been isolated and characterized. Oxidative addition of {SeC5H3(3-R)N}2 (R = H or Me) to [Pd(PP)2] (PP = dppe, dppp) gave either a mononuclear complex, [Pd{2-Se-C5H3(3-R)N}2(PP)] (for PP/R: dppe/H or Me; dppp/H) or a cationic binuclear complex, [Pd2{μ-SeC5H3(3-Me)N}2(dppp)2]2+ (4b) (R = Me) whereas reactions involving the tellurium analogue exclusively afforded trinuclear complexes, [Pd3(μ-Te)2(PP)3]Cl2 (PP = dppe (2) or dppp (6)). The latter was also obtained in the substitution reaction between [PdCl2(PP)] and NaTeC5H3(3-R)N. The substitution reactions between [PdCl2(dppe)] and Pb{EC5H3(3-R)N}2 yielded mononuclear complexes, [Pd{2-E-C5H3(3-R)N}2(dppe)] (1a–1e) (E = S, Se or Te) while in the case of [PdCl2(dppp)], the reactions resulted in the formation of mono-, bi- and tri- nuclear complexes depending on the nature of the chalcogen atom (E = S, Se or Te) and the substituent on the pyridyl ring (R = H or Me). Treatment of dipyridyl ditellurides, {TeC5H3(3-R)N}2 (R = H or Me), with [Pd(PPh3)4] gave expected tellurolate complexes, [Pd{2-TeC5H3(3-R)N}2(PPh3)2] (7a, 7b) which on prolonged standing in CDCl3 solution gave green crystals of [PdCl{2-Te(Cl)2C5H3(3-Me)N}(PPh3)] (9). The molecular structures of {TeC5H3(3-Me)N}2, [Pd2{μ-TeC5H3(3-Me)N}2(dppp)2]Cl2·3H2O (5·3H2O), [Pd3(μ-Te)2(dppp)3]Cl2·3CHCl3 (6·3CHCl3) and [PdCl{2-Te(Cl)2C5H3(3-Me)N}(PPh3)] (9) were established by single crystal X-ray diffraction analyses.

Graphical abstract: Reactivity of 2-chalcogenopyridines with palladium–phosphine complexes: isolation of different complexes depending on the nature of chalcogen atom and phosphine ligand

Supplementary files

Article information

Article type
Paper
Submitted
06 Mar 2012
Accepted
02 Oct 2012
First published
05 Oct 2012

Dalton Trans., 2013,42, 259-269

Reactivity of 2-chalcogenopyridines with palladium–phosphine complexes: isolation of different complexes depending on the nature of chalcogen atom and phosphine ligand

R. S. Chauhan, G. Kedarnath, A. Wadawale, A. M. Z. Slawin and V. K. Jain, Dalton Trans., 2013, 42, 259 DOI: 10.1039/C2DT30535F

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