Electronically Unsaturated Three-Coordinate Chloride and Methyl Complexes of Iron, Cobalt, and Nickel

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This article discusses electronically unsaturated three-coordinate chloride and methyl complexes of iron, cobalt, and nickel.

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9 p.

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Holland, Patrick L.; Cundari, Thomas R., 1964-; Perez, Lanyn L.; Eckert, Nathan A. & Lachicotte, Rene J. November 8, 2002.

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This article discusses electronically unsaturated three-coordinate chloride and methyl complexes of iron, cobalt, and nickel.

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9 p.

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Reprinted with permission from the Journal of the American Chemical Society. Copyright 2002 American Chemical Society.

Abstract: Three-coordinate organometallic complexes are rare, especially with the prototypical methyl ligand. Using a hindered, rigid bidentate ligand (L), it is possible to create 12-electron methyliron (II) and 13-electron methylcobalt (II) complexes. These complexes are thermally stable, and ¹H NMR spectra suggest that the low coordination number is maintained in solution. Attempts to create the 14-electron LNiCH₃ led instead to the three-coordinate nickel(I) complex LNi(THF). Single crystals of LMCH₃ are isomorphous with the new three-coordinate chloride complexes LNiCl and LCoCl. Along with the recently reported LFeCl (Smith, J.M.; Lachicotte, R.J.; Holland, P.L. Chem Commun. 2001, 1542), these are the only examples of three-coordinate iron(II), cobalt(II), and nickel(II) complexes with terminal chloride ligands, enabling the systematic evaluation of the effect of coordination number and metal identity on M-Cl bond lenghts. Electronic structure calculations predict the ground states of the trigonal complexes.

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  • Journal of the American Chemical Society, 2002, Washington DC: American Chemical Society, pp. 14416-14424

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  • Publication Title: Journal of the American Chemical Society
  • Volume: 124
  • Issue: 48
  • Page Start: 14416
  • Page End: 14424
  • Peer Reviewed: Yes

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  • November 8, 2002

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  • Oct. 9, 2012, 10:02 a.m.

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  • May 29, 2014, 12:05 p.m.

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Holland, Patrick L.; Cundari, Thomas R., 1964-; Perez, Lanyn L.; Eckert, Nathan A. & Lachicotte, Rene J. Electronically Unsaturated Three-Coordinate Chloride and Methyl Complexes of Iron, Cobalt, and Nickel, article, November 8, 2002; [Washington, D.C.]. (digital.library.unt.edu/ark:/67531/metadc107783/: accessed October 22, 2018), University of North Texas Libraries, Digital Library, digital.library.unt.edu; crediting UNT College of Arts and Sciences.