Combining the Reactivity Properties of PCy3 and PtBu3 into a Single Ligand, P(iPr)(tBu)2. Reaction via Mono- or Bisphosphine Palladium(0) Centers and Palladium(I) Dimer Formation

Autor:	Marialuisa Aufiero, Franziska Schoenebeck, Fabien Proutiere, Eirik Lyngvi, Italo A. Sanhueza
Rok vydání:	2014
Předmět:	Steric effects Coordination sphere Stereochemistry Ligand Organic Chemistry chemistry.chemical_element Tricyclohexylphosphine Catalysis Inorganic Chemistry chemistry.chemical_compound chemistry Polymer chemistry Reactivity (chemistry) Physical and Theoretical Chemistry Chemoselectivity Palladium
Zdroj:	Organometallics. 33:6879-6884
ISSN:	1520-6041 0276-7333
DOI:	10.1021/om5009605
Popis:	Trialkylphosphine ligands are ubiquitous in catalysis. Via modulation of the steric bulk of these ligands, two central aspects that dictate reactivity and selectivity in catalysis can be controlled: i.e., the coordination sphere and favored oxidation state of the reactive metal center. Within this class of ligands, tricyclohexylphosphine (PCy3) and tri-tert-butylphosphine (PtBu3) are most widely used in catalysis. While the smaller PCy3 favors reactivity via Pd bisphosphine species with the test substrate 4-chlorophenyl triflate 1 and does not form dinuclear Pd(I) complexes upon oxidation of Pd(0), PtBu3 reacts via a monophosphine-ligated Pd complex with 1 and forms dinuclear Pd(I) complexes on oxidation. We herein report that the hybrid ligand P(iPr)(tBu)2, characterized by a cone angle that is between those of PCy3 and PtBu3, features all of these reactivity properties in a single scaffold. This is exemplified in chemoselectivity studies with test system 1, in which the site selectivity could be readily...
Databáze:	OpenAIRE
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