Pincer-type heck catalysts and mechanisms based on PdIV intermediates: A computational study

Chemistry - A European Journal

Volumn 16, Issue 5, 2010, Pages 1521-1531

  Blacque, Olivier ^a   Frech, Christian M ^a  

^a UNIVERSITY OF ZURICH   (Switzerland)

Author keywords

Density functional calculations; Heck reaction; Palladium; Pincer complexes; Reaction mechanisms

Indexed keywords

AMINOPHOSPHINES; CATALYTIC CYCLES; CATALYTIC MECHANISMS; CATALYTIC REACTIONS; CHLORIDE LIGANDS; COMPUTATIONAL STUDIES; COUPLING PRODUCT; DENSITY-FUNCTIONAL CALCULATIONS; ENERGY PATHS; HECK REACTIONS; HIGH THERMAL STABILITY; HYDRIDE ELIMINATION; OLEFINIC BOND; OXIDATIVE ADDITIONS; PALLADIUM COMPLEXES; PALLADIUM INTERMEDIATES; PALLADIUM NANOPARTICLES; PALLADIUM PINCER-COMPLEXES; PHENYL UNITS; PINCER COMPLEXES; REACTION MECHANISM; REACTION PATHS; REACTION STEPS; RESTING STATE; STILBENE COMPLEXES;

CATALYSIS; CATALYSTS; CHLORINE COMPOUNDS; DIMETHYLFORMAMIDE; DISSOCIATION; DYES; LIGANDS; ORGANIC SOLVENTS; PALLADIUM; PHOSPHORUS COMPOUNDS; STYRENE;

PALLADIUM COMPOUNDS;

ORGANOMETALLIC COMPOUND; PALLADIUM; STILBENE DERIVATIVE;

ARTICLE; CATALYSIS; CHEMICAL STRUCTURE; CHEMISTRY; COMPUTER SIMULATION; KINETICS; STEREOISOMERISM;

CATALYSIS; COMPUTER SIMULATION; KINETICS; MOLECULAR STRUCTURE; ORGANOMETALLIC COMPOUNDS; PALLADIUM; STEREOISOMERISM; STILBENES;

EID: 75749091822     PISSN: 09476539     EISSN: 15213765     Source Type: Journal    
DOI: 10.1002/chem.200902091     Document Type: Article

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58. For cationic reaction paths see below.
59. 4a/7a, was not calculated.
60. Moreover, the formation of 6 a is even more favored by initial dissociation of the chloride ligand from la (to yield 2a) and subsequent coordination of styrene (see below).
61. -1, respectively) and confirms that complexes of type 7 are not relevant for the catalytic cycle.
62. + (2), which are the key intermediates of the catalytic cycle (see below).
63. -1 higher in energy than calculated for the isolated reactants and hence compares well with the results obtained for phenyl bromide.