期刊
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
卷 61, 期 43, 页码 -出版社
WILEY-V C H VERLAG GMBH
DOI: 10.1002/anie.202211496
关键词
Amine Borane; Carbenes; Hydrogen Storage; Magnesium; Migratory Insertion
资金
- David and Lucile Packard Foundation
- National Science Foundation Major Research Instrumentation [CHE-2018870, CHE-2102552]
- Jefferson Scholars Foundation for a Burn Family Melville Foundation Graduate Fellowship
- National Science Foundation for a Graduate Research Fellowship [1842490]
This study investigates the reaction mechanism of N-heterocyclic carbene adducts of magnesium amidoboranes through synthetic and theoretical approaches. The research reveals the occurrence of migratory insertion on the C-NHC-Mg bond in certain conditions, with observed dynamic migration of Me2N=BH2 between the Mg-N and C-NHC-Mg bonds.
A combined synthetic and theoretical investigation of N-heterocyclic carbene (NHC) adducts of magnesium amidoboranes is presented, which involves a rare example of reversible migratory insertion within a normal valent s-block element. The reaction of (NHC)Mg(N(SiMe3)(2))(2) (1) and dimethylamine borane yields the tris(amide) adduct (NHC-BN)Mg(NMe2BH3)(N(SiMe3)(2)) (2; NHC-BN = NHC-BH2NMe2). In addition to Me2N=BH2 capture at the C-NHC-Mg bond, mechanistic investigations suggest the likelihood of aminoborane migratory insertion from an RMg(NMe2BH2NMe2BH3) intermediate. To elucidate these processes, the carbene complexes (NHC)Mg(NMe2BH3)(2) (8) and (NHC)Mg(NMe2BH2NMe2BH3)(2) (9) were synthesized, and a dynamic migration of Me2N=BH2 between Mg-N and C-NHC-Mg bonds was observed in 9. This unusual reversible migratory insertion is presumably induced by dissimilar charge localization in the (-){NMe2BH2NMe2BH3} anion, as well as the capacity of NHCs to reversibly capture Me2N=BH2 in the presence of Lewis acidic magnesium species.
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