Mapping the reaction pathway in palladium-catalyzed cross-coupling reactions

Journal Article · Thu Feb 01 00:00:00 EST 1990 · Organometallics; (USA)

DOI:https://doi.org/10.1021/om00116a010· OSTI ID:7246131

Brown, J M; Cooley, N A ^[1]

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1. Dyson Perrins Lab., Oxford (England)

The formation of the cyclooctatetraene (COT) complex Pd(dppf)(COT) (dppf = 1,1{prime}-bis(diphenylphosphino)ferrocene) from Pd(dppf)X{sub 2} (X = Cl, Sr, I) and dilithium cyclooctatetraenide in situ affords an entry into the cross-coupling chemistry of this system. The reaction of Pd(dppf)(COT) with an alkenyl bromide or iodide results in the formation of the appropriate ({eta}{sup 1}-alkenyl)palladium halide via an oxidative addition of a {eta}{sup 2}-coordinated alkene species. The full characterization of the intermediate Pd(dppf)(CH{double bond}CHC{sub 6}H{sub 4}OCHY{sub 3})Br (9) and the norbornene insertion product Pd(dppf)(C{sub 7}H{sub 10}CH{double bond}CHC{sub 6}H{sub 4}OCH{sub 3}) (15) is reported. A set of putative intermediates for the coupling of alkenyl and benzyl moieties by palladium complexes is demonstrated spectroscopically. The cross-coupling cycle for the case of alkenyl-aryl coupling is delineated by an analysis of cross-coupling reactions employing {sup 13}C-labeled catalysts and unlabeled substrates (and vice versa). Platinum analogues of all the intermediates in this cross-coupling catalytic cycle have been observed.

• OSTI ID: 7246131
• Journal Information: Organometallics; (USA), Vol. 9:2; ISSN 0276-7333
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC
ORGANIC
PHYSICAL AND ANALYTICAL CHEMISTRY
PALLADIUM COMPLEXES
CHEMICAL REACTION KINETICS
CALCULATION METHODS
CATALYSIS
COUPLING
DATA ANALYSIS
EXPERIMENTAL DATA
FERROCENE
MEASURING INSTRUMENTS
MEASURING METHODS
COMPLEXES
DATA
DIENES
HYDROCARBONS
INFORMATION
IRON COMPLEXES
KINETICS
NUMERICAL DATA
ORGANIC COMPOUNDS
POLYENES
REACTION KINETICS
TRANSITION ELEMENT COMPLEXES
400201* - Chemical & Physicochemical Properties