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Unusual Magnetism of an Unsymmetrical Trinickel Chain

  1. F. Albert Cotton1,†,
  2. Carlos A. Murillo1,
  3. Qingsheng Wang1,2,
  4. Mark D. Young1

Article first published online: 20 OCT 2008

DOI: 10.1002/ejic.200800808

Issue

European Journal of Inorganic Chemistry

European Journal of Inorganic Chemistry

Volume 2008, Issue 33, pages 5257–5262, November 2008

Additional Information

How to Cite

Cotton, F. A., Murillo, C. A., Wang, Q. and Young, M. D. (2008), Unusual Magnetism of an Unsymmetrical Trinickel Chain. Eur. J. Inorg. Chem., 2008: 5257–5262. doi: 10.1002/ejic.200800808

Author Information

  1. 1

    Laboratory for Molecular Structure and Bonding, Department of Chemistry, Texas A&M University, College Station, Texas 77842-3012, USA

  2. 2

    Mary Kay O'Connor Process Safety Center, Artie McFerrin Department of Chemical Engineering, Texas A&M University, College Station, Texas 77843-3122, USA

  1. †

    Deceased on February 20, 2007. This article is dedicated to the memory of Professor F. Albert Cotton.

Publication History

  1. Issue published online: 11 NOV 2008
  2. Article first published online: 20 OCT 2008
  3. Manuscript Received: 13 AUG 2008

Funded by

  • Robert A. Welch Foundation
  • Texas A&M University
  • National Science Foundation (NSF)

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Keywords:

  • Extended metal atom chain, EMAC;
  • Nickel compounds;
  • Magnetism;
  • Square-planar and square-pyramidal arrangements

Abstract

An extended metal atom chain (EMAC) compound with an unsymmetrical trinickel core and the formula [Ni3(dpa)4(CH3CN)](PF6)2·2CH2Cl2 (1·2CH2Cl2, dpa is the anion of 2,2′-dipyridylamine) has the central Ni atom in an essentially square-planar configuration. Besides having four equatorial nitrogen atoms, the two terminal metal centers have axial interactions that are notably different with one having a strongly bound acetonitrile molecule with a Ni(3)–N(3) distance of 2.108(5) Å while the other unit has a very weak interaction with an axial PF6 anion [Ni(1)···F(1) separation of 2.690 Å]. In these outer units, the Ni(3) atom is pulled out of the idealized plane of the four equatorial nitrogen atoms by 0.239 Å, while in the one with an axial PF6 anion the metal atom is pulled from the plane of the equatorial nitrogen atoms by only 0.097 Å. In 1 there are two unpaired electrons and an S = 1 state prevails from ca. 25 to 300 K. This magnetic behavior differs considerably from that of symmetrical trinickel EMACs with two strongly pyramidal terminal nickel atoms. A discussion of the effect of various axial ligands on the geometry of the terminal nickel atoms is provided. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2008)

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