1083211-26-0Relevant articles and documents
Reactions of palladium(0) olefin complexes stabilized by some different hetero- and homo-ditopic spectator ligands with propargyl halides
Canovese, Luciano,Scattolin, Thomas,Visentin, Fabiano,Santo, Claudio
, p. 10 - 21 (2017)
Several new allenyl and propargyl complexes have been obtained by oxidative addition with propargyl chlorides of palladium (0) olefin complexes stabilized by N?N, P?P, N?P, N?S. and N?C homo? and hetero?ditopic spectator ligands. The oxidative addition of some of the isolated palladium(0) olefin derivatives with 3?chloro?1?propyne and 3?chloro?1? phenyl?propyne has been investigated and the ensuing tautomeric mixtures bearing propargyl and allenyl fragmenst η1? coordinated isolated. As a consequence of a detailed kinetic study, we have analyzed the influence of the electronic and steric parameters of the involved reactants and hypothesized the mechanism of reaction. The tautomeric rearrangement of one allenyl isomer into its propargyl counterpart was also investigated and in this case the complete determination of all the rate constants involved has been obtained. Beside these studies, two very rare η3?propargyl palladium derivatives have been isolated and characterized.
The role of ancillary ligands and of electron poor alkenes and alkynes in stabilizing Pd(0) derivatives: A comparative study
Canovese, Luciano,Visentin, Fabiano,Santo, Claudio,Dolmella, Alessandro
, p. 411 - 419 (2009/04/12)
The peculiar characteristics of the ligand neocuproine (2,9-dimethylphenanthroline) allow a number of exchange equilibrium studies between the low valence complex [Pd(η2-nq)(Neocup)] (nq = naphthoquinone; Neocup = neocuproine) and several alken
Transmetalation reactions. The role of the stabilizing olefin in determining the overall reaction rate
Canovese, Luciano,Visentin, Fabiano,Levi, Carlo,Santo, Claudio
, p. 3324 - 3330 (2008/12/22)
A systematic study concerning the transmetalation reaction between the palladium butadienyl complexes [PdCl((ZC{double bond, long}CZ)2Me)(L-L′)] (Z = COOMe; L-L′ = MeN-SPh (1A), N-SPh (1B), DPPQ-Me (1C), BiPy (1D), DPPE (1E)) and tributyl-phenylethynyl-stannane in the presence of some stabilizing olefins (ma, fn, nq, dmfu, and tmetc) was undertaken. The dependence of the reaction rate on the nature of the ancillary ligand was discussed in terms of the donor capability and steric characteristics of the ligand. It has been noticed that, other things being equal, the joined distorted MeN-SPh ligand imparts the highest reactivity to its derivative (complex 1A). The most surprising issue was however represented by the olefin which seems to affect heavily the reactivity of the starting substrate thereby increasing the overall reaction rate. The most active olefins were ma and fn. In the case of the reaction between the complex 1A and tributyl-phenylethynyl-stannane in the presence of fn an exhaustive kinetic study was carried out and a mechanistic hypothesis was advanced.
