Studies of Low-Coordinate Iron Dinitrogen Complexes

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This article discusses low-coordinate iron dinitrogen complexes. Understanding the interaction of N₂ with iron is relevant to the iron catalyst used in the Haber process and to possible roles of the FeMoco active site of nitrogenase.

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14 p.

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Smith, Jeremy M.; Sadique, Azwana R.; Cundari, Thomas R., 1964-; Rodgers, Kenton R.; Lukat-Rodgers, Gudrun; Lachicotte, Rene J. et al. December 31, 2005.

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This article discusses low-coordinate iron dinitrogen complexes. Understanding the interaction of N₂ with iron is relevant to the iron catalyst used in the Haber process and to possible roles of the FeMoco active site of nitrogenase.

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14 p.

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Reprinted with permission from the Journal of the American Chemical Society. Copyright 2005 American Chemical Society.

Abstract: The work reported here uses synthetic compounds to evaluate the extent of NN weakening in low-coordinate iron complexes with an FeNNFe core. The steric effects, oxidation level, presence of alkali metals, and coordination number of the iron atoms are varied, to gain insight into the factors that weaken the NN bond. Diiron complexes with a bridging N2 ligand, LRFeNNFeLR (LR = β-diketiminate; R = Me, tBu), result from reduction of [LRFeCl]n under a dinitrogen atmosphere, and an iron(I) precursor of an N2 complex can be observed. X-ray crystallographic and resonance Raman data for LRFeNNFeLR show a reduction in the N-N bond order, and calculations (density functional and multireference) indicate that the bond weakening arises from cooperative back-bonding into the N2 π* orbitals. Increasing the coordination number of iron from three to four through binding of pyridines gives compounds with comparable N-N weakening, and both are substantially weakened relative to five-coordinate iron-N2 complexes, even those with a lower oxidation state. Treatment of LRFeNNFeLR with KC8 gives K2LRFeNNFeLR, and calculations indicate that reduction of the iron and alkali metal coordination cooperatively weaken the N-N bond. The complexes LRFeNNFeLR react as iron(I) fragments, losing N2 to yield iron(I) phosphine, CO, and benzene complexes. They also reduce ketones and aldehydes to give the products of pinacol coupling. The K2LRFeNNFeLR compounds can be alkylated at iron, with loss of N2.

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  • Journal of the American Chemical Society, 2005, Washington DC: American Chemical Society, pp. 756-769

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  • Publication Title: Journal of the American Chemical Society
  • Volume: 128
  • Page Start: 756
  • Page End: 769
  • Pages: 14
  • Peer Reviewed: Yes

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  • December 31, 2005

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  • March 2, 2012, 11:47 a.m.

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  • July 23, 2013, 12:02 p.m.

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Smith, Jeremy M.; Sadique, Azwana R.; Cundari, Thomas R., 1964-; Rodgers, Kenton R.; Lukat-Rodgers, Gudrun; Lachicotte, Rene J. et al. Studies of Low-Coordinate Iron Dinitrogen Complexes, article, December 31, 2005; [Washington, D.C.]. (digital.library.unt.edu/ark:/67531/metadc77137/: accessed December 15, 2017), University of North Texas Libraries, Digital Library, digital.library.unt.edu; crediting UNT College of Arts and Sciences.