期刊
ACS CATALYSIS
卷 5, 期 2, 页码 622-626出版社
AMER CHEMICAL SOC
DOI: 10.1021/cs501639r
关键词
cobalt; hydroboration; catalysis; redox-active ligands; boronates
资金
- Princeton University
- US National Science Foundation (NSF) [CHE-1265988]
- Merck
- Division Of Chemistry
- Direct For Mathematical & Physical Scien [1265988] Funding Source: National Science Foundation
Cobalt alkyl complexes bearing readily available and redox-active 2,2':6',2-terpyridine and a-diimine ligands have been synthesized, and their electronic structures have been elucidated. In each case, the supporting chelate is reduced to the monoanionic, radical form that is engaged in antiferromagnetic coupling with the cobalt(II) center. Both classes of cobalt alkyls proved to be effective for the isomerization hydroboration of sterically hindered alkenes. An a-diimine-substituted cobalt allyl complex proved exceptionally active for the reduction of hindered tri-, tetra-, and limonene, formation of an eta(3)-allyl complex with a C-H agostic interaction was identified and accounts for the sluggish reactivity observed with diene substrates. For the terpyridine derivative, unique Markovnikov selectivity with styrene was also observed with HBPin.
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