Journal
ORGANOMETALLICS
Volume 36, Issue 2, Pages 363-371Publisher
AMER CHEMICAL SOC
DOI: 10.1021/acs.organomet.6b00792
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Funding
- U.S. Department of Energy, Office of Science, Basic Energy Sciences [DE-SC0008058]
- U.S. Department of Education
- U.S. Department of Energy (DOE) [DE-SC0008058] Funding Source: U.S. Department of Energy (DOE)
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Presented herein is a general design strategy for the formation of coordinatively unsaturated Mn(I) fragments via the cis labilization of CO using metal carboxylates and subsequent deprotection by a range of abstraction agents. A consistent trend is observed in the ability of carboxylate ligands to facilitate CO dissociation as a function of the electron-releasing properties of the carboxylate R group. This is in agreement with previous theoretical work on cis-labilizing ligands. A variety of K-2-coordinated carboxylates function as site-protection ligands for the [Mn(CO)(2)(CNArDIPP2)(2)](+) scaffold and can be liberated using a range of synthetic techniques. The coordinatively unsaturated species thus formed are shown to be strong metal-based Lewis acids and can engage in agostic-type interactions; in addition, they can be trapped as the corresponding solvento complexes by ethereal solvents.
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