Group-Transfer Reactions of Nickel-Carbene and -Nitrene Complexes with Organoazides and Nitrous Oxide that Form New C=N, C=O, and N=N Bonds

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This article discusses group-transfer reactions of nickel-carbene and -nitrene complexes with organoazides and nitrous oxide that form new C=N, C=O, and N=N bonds.

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2 p.

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Harrold, Nicole D.; Waterman, Rory; Hillhouse, Gregory L. & Cundari, Thomas R., 1964- August 19, 2009.

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This article discusses group-transfer reactions of nickel-carbene and -nitrene complexes with organoazides and nitrous oxide that form new C=N, C=O, and N=N bonds.

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2 p.

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Reprinted with permission from the Journal of the American Chemical Society. Copyright 2009 American Chemical Society.

Abstract: 1-Adamantyl- and mesitylazide react with (dtbpe)Ni=CPh2 (1; dtbpe = 1,2-bis(di-tert-butylphosphino)ethane) at ambient temperature to give the ketimines RN=CPh2 (2a, R = Mes; 2b, R = Ad) in high yield. Kinetic studies for the reaction of 1 with N3Ad yield activation parameters of ∆H‡ = +8(±1) kcal/mol and ∆S‡ = -44(±3) cal/(mol•K). Treatment of 1 with N2O at low temperature results in clean conversion to the benzophenone complex (dtbpe)Ni=NR (4a, R = Mes; 4b, R = Ad) react with N3Mes and N3Ad at ambient temperature to give the diazenes RN=NR (6a, R = Mes; 6b, R = Ad) in good yield. B3LYP/6-311+G(d) calculations support a mechanism for all three reactions that features 1,3-dipolar cycloaddition to give five-membered ring (Huisgen) intermediates, followed by N2 elimination to give the products. Calculated activation parameters for the reaction of (dhpe)Ni=CH2 (dhpe = 1,2-bis(dihydridophosphino)ethane) with N3Me compare well with the experimental values.

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  • Journal of the American Chemical Society, 2009, Washington D.C.: American Chemical Society, pp. 12872-12873

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  • Publication Title: Journal of the American Chemical Society
  • Volume: 131
  • Issue: 36
  • Page Start: 12872
  • Page End: 12873
  • Peer Reviewed: Yes

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  • August 19, 2009

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  • Oct. 9, 2012, 10:02 a.m.

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  • Jan. 9, 2015, 5:09 p.m.

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Harrold, Nicole D.; Waterman, Rory; Hillhouse, Gregory L. & Cundari, Thomas R., 1964-. Group-Transfer Reactions of Nickel-Carbene and -Nitrene Complexes with Organoazides and Nitrous Oxide that Form New C=N, C=O, and N=N Bonds, article, August 19, 2009; [Washington, D.C.]. (digital.library.unt.edu/ark:/67531/metadc107794/: accessed September 23, 2018), University of North Texas Libraries, Digital Library, digital.library.unt.edu; crediting UNT College of Arts and Sciences.