869966-69-8

Upstream product

• 108-31-6 maleic anhydride 
• 858132-94-2 [PdCl(8-diphenylphosphanyl-2-methylquinoline)(C(COOMe)C(COOMe)C(COOMe)C(Me)COOMe)] 
• 52522-40-4 tris(dibenzylideneacetone)dipalladium⁽⁰⁾ chloroform complex 
• 478548-99-1 2-methyl-8-(diphenylphosphino)quinoline 

Relevant academic research and scientific papers

Transmetalation reactions. The role of the stabilizing olefin in determining the overall reaction rate

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.

Attack of substituted alkynes on olefin palladium(O) derivatives of pyridylthioethers. The first kinetic study on the mechanism of formation of palladacyclopentadiene complexes

The formation of metallacyclopentadienyl derivatives was studied under controlled conditions, and the kinetics and mechanism of reactions between pyridylthioether olefin Pd(0) substrates and substituted alkynes of the type ZC=CZ (Z = COOMe, COOEt, COOt-Bu) leading to the corresponding palladacyclopentadienyl species were systematically investigated. In the case of less hindered ancillary ligands the attack of the alkyne forming a reactive monoalkyne intermediate was found to be the rate-determining step. In this respect the rates of reaction were discussed in terms of the substituent-induced basicity-of sulfur and nitrogen of the ancillary ligands. The associative nature of the attack was unequivocally established, and the formation of a transition state bearing a monodentate ancillary ligand was proposed. In the case of more hindered ancillary ligands a partially stabilized monoalkyne intermediate is formed irrespective of the olefin in the starting complex, and this species strongly influences the reaction progress. Formation of hexamethylmellitate under mild conditions is also observed.