Dissecting Transmetalation Reactions at the Molecular Level: Role of the Coordinated Anion in Gas-Phase Models for the Transmetalation Step of the Hiyama Cross-Coupling Reaction

• Published in: Organometallics Vol. 40; no. 12; pp. 1822 - 1829
• Main Authors: Stewart, Adam W. E, Ma, Howard Z, Weragoda, Geethika K, Khairallah, George N, Canty, Allan J, O’Hair, Richard A. J
• Format: Journal Article
• Language: English
• Published: American Chemical Society 28.06.2021
• ISSN: 0276-7333; 1520-6041
• DOI: 10.1021/acs.organomet.0c00795

Palladium-catalyzed cross-coupling protocols have become a cornerstone in organic synthesis. Here, a gas-phase model of the Hiyama cross-coupling reaction was designed to shed light on the roles of coordinated anions (fluoride versus chloride) in transmetalation from Si to Pd. A combination of mass spectrometry experiments and DFT calculations was used. The ligated palladium fluoride and chloride cationic complexes, [(phen)­Pd­(X)]+ (X = F and Cl), readily react with vinyltrimethylsilane, Me3Si­(CHCH2), via transmetalation to give [(phen)­Pd­(CHCH2)]+ as the major product. DFT calculations reveal that this transmetalation reaction is concerted and proceeds via a four-centered transition state, illustrating the role of coordinated halide in this gas-phase system. Two minor side products are observed corresponding to transmetalation to give [(phen)­Pd­(CH3)]+ and [(phen)­Pd­(SiMe2X)]+. DFT calculations suggest that these arise from the same initial Si to Pd methyl transmetalation pathway to give the [(phen)­Pd­(CH3) + Me2(CHCH2)­SiX]+ intermediate, which either then loses Me2(CHCH2)­SiX or reacts via C–C bond coupling to ultimately yield propene and [(phen)­Pd­(SiMe2X)]+. [(phen)­Pd­(CHCH2)]+ undergoes a reaction with a second molecule of vinyltrimethylsilane to form an adduct, which upon collision-induced dissociation liberates 1,3-butadiene to form [(phen)­Pd­(SiMe3)]+. DFT calculations suggest a mechanism in which C–C bond formation is followed by migration of SiMe3 from C to Pd. Links between the observed gas-phase chemistry and solution-phase Pd-mediated homocoupling reactions of vinyltrimethylsilanes are explored.