Witayapaisitsan N.Worakul T.Surawatanawong P.Mahidol University2025-02-262025-02-262025-01-01Inorganic Chemistry (2025)00201669https://repository.li.mahidol.ac.th/handle/123456789/105445The 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.ChemistryArticleSCOPUS10.1021/acs.inorgchem.4c055172-s2.0-852181503111520510X