期刊
ACCOUNTS OF CHEMICAL RESEARCH
卷 48, 期 6, 页码 1696-1702出版社
AMER CHEMICAL SOC
DOI: 10.1021/acs.accounts.5b00036
关键词
-
资金
- National Science Foundation CAREER Grant [CHE-0134658]
- Department of Energy, Office of Basic Energy Sciences [DE-FG02-09ER16089]
Inexpensive base metals are more affordable and sustainable than precious metals and also offer opportunities to discover new mechanisms for selective catalytic reactions. Base metal complexes can have high-spin electronic configurations that are rare in precious metal complexes. This Account describes some concepts relevant to high-spin organometallic complexes, focusing on our recent work with beta-diketiminate complexes of iron and cobalt. Even though high-spin organometallic complexes have some unfamiliar spectroscopic properties, they can be studied using NMR spectroscopy as well as techniques that focus on the magnetism brought about by the unpaired electrons. Understanding the mechanisms of reactions using these complexes can be complicated, because complexes with a high-spin electronic configuration may need to change spin states to avoid high barriers for reaction. These spin-state changes can be rapid, and the ability of an excited spin state to cut through the barrier for a reaction can lead to spin acceleration. These concepts, originally developed by Poll, Shaik, Schwarz, and Harvey, are applied here to the fundamental organometallic reaction of beta-hydride elimination (BHE). Experimentally validated density-functional calculations show spin acceleration in BHE using three-coordinate iron(II) and cobalt(II) complexes. A square-planar transition state is particularly beneficial for accelerating BHE when a high-spin iron(II) complex goes from an S = 2 ground state to an S = 1 transition state or when a high-spin cobalt(II) complex goes from an S = 3/2 ground state to an S = 1/2 transition state. The relative energies of the spin states can be controlled with the choice of the supporting ligand. Using an appropriate ligand, isomerization of 1-alkenes to their Z-2 isomers can be catalyzed in high yields using the cobalt(II) alkyl complexes as catalysts. Though an earlier paper attributed the regioselectivity and stereoselectivity to the preferred geometry of the BHE step, the results of isotope labeling experiments suggest that the selectivity may actually come from the alkene exchange step (again with spin acceleration). In general, the use of multiple intersecting spin states is envisioned as a profitable strategy for bringing about low reaction barriers and high selectivity in catalytic reactions. This effort requires high-accuracy computational models as well as ligand design that gives nearby spin states with appropriate geometries.
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