Mechanistic Insights into Ru-S Complex-Catalyzed C-H Silylation and Borylation of N-Heteroarene: Distinct Bonding Interactions
Issued Date
2025-01-01
Resource Type
ISSN
00201669
eISSN
1520510X
Scopus ID
2-s2.0-85218150311
Journal Title
Inorganic Chemistry
Rights Holder(s)
SCOPUS
Bibliographic Citation
Inorganic Chemistry (2025)
Suggested Citation
Witayapaisitsan N., Worakul T., Surawatanawong P. Mechanistic Insights into Ru-S Complex-Catalyzed C-H Silylation and Borylation of N-Heteroarene: Distinct Bonding Interactions. Inorganic Chemistry (2025). doi:10.1021/acs.inorgchem.4c05517 Retrieved from: https://repository.li.mahidol.ac.th/handle/123456789/105445
Title
Mechanistic Insights into Ru-S Complex-Catalyzed C-H Silylation and Borylation of N-Heteroarene: Distinct Bonding Interactions
Author(s)
Author's Affiliation
Corresponding Author(s)
Other Contributor(s)
Abstract
The silylation and borylation of N-heteroarenes are essential processes for preparing key building blocks in organic synthesis. The Ru-S complex 1, [(PEt3)Ru(DmpS)]+ (DmpS = 2,6-dimesitylphenyl thiolate), catalyzes both C-H silylation and borylation of N-heteroarenes. Herein, we performed a density functional study to investigate the mechanisms of 1 catalyzed C-H silylation of 1-methylindole using hydrosilanes and C-H borylation using dialkoxyhydroborane (HBpin) and dialkylhydroborane (9BBN). The mechanism involves four main steps: (i) Si-H/B-H activation, (ii) silyl/boryl transfer to 1-methylindole, (iii) proton abstraction to yield the silylated/borylated product, and (iv) H2 elimination to regenerate complex 1. The rate-determining step is silyl/boryl transfer. Notably, upon B-H activation, the B-H bond of HBpin is fully cleaved, while the B-H bond of 9BBN remains partially intact. Moreover, instead of forming silylium/borenium ions, the Si-H and B-H activations lead to distinct Si-H/B-H-activated complexes: (i) thiosilane/thioborane-supported Ru-H complexes for hydrosilane and HBpin and (ii) a three-center two-electron Ru-H-B complex for 9BBN. Differences in bonding interactions affect the energy barriers in the silyl/boryl transfer. Insights into these electronic structures provide a foundation for designing metal-ligand cooperative catalysts for C-H silylation and borylation of N-heteroarenes.