Carreras, Javier published the artcileExploiting the π-acceptor properties of carbene-stabilized phosphorus centered trications [L3P] 3+: applications in Pt(II) catalysis, Computed Properties of 849052-15-9, the publication is Journal of the American Chemical Society (2012), 134(40), 16753-16758, database is CAplus and MEDLINE.
2-Ethynylbiaryls undergo 6-endo-dig cyclization into annulated phenanthrenes and helicenes, catalyzed by platinum complex with electron-accepting tricationic cyclopropenylium phosphine, [(Me2N)2C3+]3P (1), [[(Me2N)2C3+]3PPtCl3][ClO4]2 (3). The complex 3 is a bench-stable compound, easily available from reaction of K2PtCl4 with 1; the complex 3 is an excellent catalyst for cyclization of 2-ethynylbiaryls, when activated by Ag[CB11H6Cl6]. Complexation of platinum complex (3) with alkyne is approx. 6 kcal mol-1 more favorable, than with triphenylphosphine analog [(PPh3)PtCl3]–. This constitutes the first example ever reported of using a P1-centered trication as ligand in catalysis. The strong π-acceptor character of 1 that derives from its three pos. charges substantially increases the intrinsic π-acidity of Pt in complex 1·PtCl2 and dramatically enhances its ability to activate π-systems toward nucleophilic attack. As a consequence, a remarkable acceleration of the model transformation is observed when compared with other classical π-acceptor ligands such as P(OPh)3 or P(C6F5)3. Moreover, the employment of 1 as ligand also expands the scope of this reaction to previously inaccessible substitution patterns. Kinetic studies and deuterium labeling experiments as well as d. functional theory (DFT) calculations were performed in order to explain these findings.
Journal of the American Chemical Society published new progress about 849052-15-9. 849052-15-9 belongs to chlorides-buliding-blocks, auxiliary class Chloride,Boronic acid and ester,Benzene,Ether,Boronic Acids,Boronic Acids,Boronic acid and ester,, name is (4-((2-Chlorobenzyl)oxy)-3,5-dimethylphenyl)boronic acid, and the molecular formula is C15H16BClO3, Computed Properties of 849052-15-9.
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