190002-29-0Relevant academic research and scientific papers
Polymer producing palladium complexes of unidentate phosphines in the methoxycarbonylation of ethene
Smith, Graeme,Vautravers, Nicolas R.,Cole-Hamilton, David J.
, p. 872 - 877 (2009/06/20)
A wide range of unidentate phosphines have been studied as ligands for the palladium-catalysed methoxycarbonylation of ethene in the presence of methanesulfonic acid using methanol as the solvent. At high phosphine to Pd ratios, methyl propanoate is forme
Comparison of the Reactivities of Neutral and Cationic Organopalladium Complexes toward CO, Isocyanides, and Olefins
Kayaki, Yoshihito,Shimizu, Isao,Yamamoto, Akio
, p. 917 - 927 (2007/10/03)
Cationic solvent-coordinated organopalladium complexes [PdR(solvent)(L)2]+A- 2 (R = organic group, L = tertiary phosphine, A = counter anion such as BF4, PF6, and triflate) have been prepared by removal of the halide ligand X in neutral complexes. [PdR(X)(L)2] 1 with an equimolar amount of silver salt. The cationic complexes 2 show much greater rates of CO insertion than the parent neutral complexes 1. Comparison of the reactivities of 2 and of the other cationic complexes [PdMe(Y)(L)2]+ (Y = strongly coordinating ligand such as tertiary phosphine, pyridine, and isocyanide) toward CO insertion indicates that availability of the site for incoming CO is a dominant factor in determining their reactivities. In contrast, insertion of isocyanides into Pd-C bond is not hindered by occupation of the vacant site in the organopalladium complexes. Successive hetero-insertions of isocyanide and CO into Mc-Pd bond, i.e., CO insertion into the 1-iminoalkyl-Pd bond and isocyanide insertion into the acetyl-Pd, were realized. Olefins were found not to undergo the insertion into Pd-Me bond in phosphine-coordinated complexes, whereas insertion of methyl acrylate into the Me-Pd bond in a cationic complex having bipyridine ligand was observed.
