Barium-Catalysed Dehydrocoupling of Hydrosilanes and Borinic Acids: A Mechanistic Insight.
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ArticleAuthors
Le Coz, ErwannZhang, Ziyun
Roisnel, Thierry
Cavallo, Luigi

Falivene, Laura

Carpentier, Jean-François

Sarazin, Yann

KAUST Department
Chemical Science ProgramKAUST Catalysis Center (KCC)
Physical Science and Engineering (PSE) Division
Date
2020-02-25Online Publication Date
2020-02-25Print Publication Date
2020-03-18Embargo End Date
2021-02-26Submitted Date
2019-10-29Permanent link to this record
http://hdl.handle.net/10754/660449
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Two very rare cases of barium boryloxides, the homoleptic [Ba(OB{CH(SiMe3)2}2)2⋅C7H8] and the heteroleptic [{LONO4}BaOB{CH(SiMe3)2}2] stabilised by the multidentate aminoetherphenolate {LONO4}−, are presented, and their structural properties are discussed. The electron-deficient [Ba(OB{CH(SiMe3)2}2)2⋅C7H8] shows, in particular, resilient η6-coordination of the toluene molecule. Together with its amido parents [Ba{N(SiMe3)2}2⋅thf2] and [Ba{N(SiMe3)2}2]2, this complex catalyses the fast and chemoselective dehydrocoupling of borinic acids R2BOH and hydrosilanes HSiR′3, yielding borasiloxanes R2BOSiR′3 in a controlled fashion. The assessment of substrate scope indicates that, for now, the reaction is limited to bulky borinic acids. Kinetic analysis shows that the rate-limiting step of the catalytic manifold traverses a dinuclear transition state. A detailed mechanistic scenario is proposed on the basis of DFT computations, the results of which are fully consistent with experimental data. It consists of a stepwise process with rate-determining nucleophilic attack of a metal-bound O-atom onto the incoming hydrosilane, involving throughout dinuclear catalytically active species.Citation
Le Coz, E., Zhang, Z., Roisnel, T., Cavallo, L., Falivene, L., Carpentier, J., & Sarazin, Y. (2020). Barium-Catalysed Dehydrocoupling of Hydrosilanes and Borinic Acids: A Mechanistic Insight. Chemistry – A European Journal. doi:10.1002/chem.201904933Sponsors
L.C., L.F. and Z.Z. thank the King Abdullah University of Science and Technology (KAUST) for supporting this work. For computer time, this research used the resources of the KAUST Super-computing Laboratory (KSL) at KAUST. E.L.C. thanks the Univer-sity of Rennes 1 for a PhD grant.Publisher
WileyAdditional Links
https://onlinelibrary.wiley.com/doi/abs/10.1002/chem.202000478ae974a485f413a2113503eed53cd6c53
10.1002/chem.201904933