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Palladium Round Trip in the Negishi Coupling of trans ‐[PdMeCl(PMePh 2 ) 2 ] with ZnMeCl: An Experimental and DFT Study of the Transmetalation Step
Author(s) -
Fuentes Beatriz,
GarcíaMelchor Max,
Lledós Agustí,
Maseras Feliu,
Casares Juan A.,
Ujaque Gregori,
Espinet Pablo
Publication year - 2010
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201001332
Subject(s) - transmetalation , negishi coupling , palladium , coupling (piping) , engineering , chemistry , organic chemistry , mechanical engineering , catalysis
Gets there in the end : The large rate difference of the slow reductive elimination and the fast transmetalation–retrotransmetalation steps allows Pd to visit complexes 3, 2 , and 1 many times before coupling from 2 takes place. This fast recurrence of transformations offers many opportunities for the formation of undesired homocoupling products in Negishi reactions by statistically accessible “mistaken” retrotransmetalation events in the multitude of processes preceding the slower irreversible reductive elimination of the coupling product.