Calcium Hydride Cation Dimer Catalyzed Hydrogenation of Unactivated 1-Alkenes and H₂ Isotope Exchange: Competitive Ca-H-Ca Bridges and Terminal Ca-H Bonds.

ABSTRACT: Recently, it was shown that the double Ca-H-Ca bridged calcium hydride cation dimer complex [LCaH₂ CaL]²⁺ (macrocyclic ligand L=NNNN-tetradentate Me₄ TACD) exhibited remarkable activity in catalyzing the hydrogenation of unactivated 1-alkenes as well as the H₂ isotope exchange under mild conditions, tentatively via the terminal Ca-H bond of cation monomer LCaH⁺ . In this DFT mechanistic work, a novel substrate-dependent catalytic mechanism is disclosed involving cooperative Ca-H-Ca bridges for H₂ isotope exchange, competitive Ca-H-Ca bridges and terminal Ca-H bonds for anti-Markovnikov addition of unactivated 1-alkenes, and terminal Ca-H bonds for Markovnikov addition of conjugation-activated styrene. THF-coordination plays

SUBMITTER: Qu ZW 

PROVIDER: S-EPMC10100058 | biostudies-literature | 2023 Jan

REPOSITORIES: biostudies-literature