Mechanistic Study of Oxy Insertion into Nickel Carbon Bonds with Nitrous Oxide

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Article discussing a mechanistic study of oxy insertion into nickel carbon bonds with nitrous oxide.

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7 p.: ill.

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Figg, Travis M. & Cundari, Thomas R., 1964- Creation Date: Unknown.

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Article discussing a mechanistic study of oxy insertion into nickel carbon bonds with nitrous oxide.

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7 p.: ill.

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Reprinted with permission from Organometallics. Copyright 2012 American Chemical Society.

Abstract: Transition-metal-mediated oxy insertion into metal carbon bonds is useful for the development of catalytic cycles for selective hydrocarbon oxidation. However, there are few bona fide examples of net oxy insertion with transition-metal complexes. An extremely rare example of a 3d metal mediating oxy insertion into metal carbon bonds is a series of Niᴵᴵ alkyl complexes reacting with nitrous oxide (N₂0) reported by Hillhouse and co-workers; however, the mechanism was never fully elucidated. A computational study has been performed on bipyridyl nickel metallacycles that form nickel alkoxides upon reaction with N₂0 to attain insight into future catalyst design for oxygen atom transfer reactions. Two possible mechanisms are explored. Of the two pathways, the computations suggest that the preferred mechanism proceeds through a Ni oxyl intermediate followed by alkyl migration of the nickel carbon bond to form an alkoxide. Oxyl formation was found to be the rate-determining step, with a free energy barrier of 29.4 kcal/mol for bpyNiᴵᴵ(cyclo-(CH₂)₄). Complexes that contain sp²-hybridized molecules at the β-carbon site within the metallacycle ring do not undergo oxy insertion due to elevated barriers. While exploring insertion with another oxidant, namely pyridine N-oxide, we found that N₂0 is critical for net oxy insertion with this complex due to the substantial thermodynamic advantage of N₂ expulsion. Reaction with pyridine N-oxide necessitated expulsion of a "worse" leaving group, resulting in much higher barriers (ΔG = 49.7 kcal/mol) for the oxyl formation step.

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  • Organometallics, 2012, Washington DC: American Chemical Society, pp. 4998-5004

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  • Publication Title: Organometallics
  • Volume: 31
  • Issue: 14
  • Page Start: 4998
  • Page End: 5004
  • Peer Reviewed: Yes

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  • July 5, 2012

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  • Sept. 13, 2013, 2:58 p.m.

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  • April 2, 2014, 4 p.m.

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Figg, Travis M. & Cundari, Thomas R., 1964-. Mechanistic Study of Oxy Insertion into Nickel Carbon Bonds with Nitrous Oxide, article, Date Unknown; [Washington, DC]. (digital.library.unt.edu/ark:/67531/metadc181680/: accessed September 24, 2017), University of North Texas Libraries, Digital Library, digital.library.unt.edu; crediting UNT College of Arts and Sciences.