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Dispersion Force Stabilized Two-coordinate Transition Metal-Amido Complexes of the -N(SiMe₃)Dipp (Dipp = C₆H₃-2,6-Pri₂) Ligand: Structural, Spectroscopic, Magnetic, and Computational Studies
Inorganic Chemistry
  • Chun-Yi Lin
  • Jingdong Guo
  • James C. Fettinger
  • Shigeru Nagase
  • Fernande Grandjean, Missouri University of Science and Technology
  • Gary J. Long, Missouri University of Science and Technology
  • Nicholas F. Chilton
  • Philip P. Power
Abstract

A series of high spin, two-coordinate first row transition metal–amido complexes, M{N(SiMe3)Dipp}2 {M = Fe (1), Co (2), or Ni (3); Dipp = C6H3-2,6-Pri2} and a tetranuclear C–H activated chromium amide, [Cr{N(SiMe2CH2)Dipp}2Cr]2(THF) (4), were synthesized by reaction of their respective metal dihalides with 2 equiv of the lithium amide salt. They were characterized by X-ray crystallography, electronic and infrared spectroscopy, SQUID magnetic measurements, and computational methods. Contrary to steric considerations, the structures of 13 display planar eclipsed M{NSiC(ipso)}2 arrays and short M–N distances. DFT calculations, corrected for dispersion effects, show that dispersion interactions involving C–H–H–C moieties likely stabilize the structures by 21.1–29.4 kcal mol–1, depending on the level of the calculations employed. SQUID measurements confirm high spin electron configurations for all the complexes and substantial orbital contributions for 1 and 2.

Department(s)
Chemistry
Sponsor(s)
National Science Foundation (U.S.)
Grant-in-Aid for Specially Promoted Research
Comments
Financial support by National Science Foundation (U.S.), Grant No. CHE-1263760; and Grant-in-Aid for Specially Promoted Research, Grant No. 22000009.
Electronic OCLC #
37637103
Print OCLC #
1753164
Document Type
Article - Journal
Document Version
Citation
File Type
text
Language(s)
English
Rights
© 2013 American Chemical Society (ACS), All rights reserved.
Publication Date
12-1-2013
Publication Date
01 Dec 2013
Disciplines
Citation Information
Chun-Yi Lin, Jingdong Guo, James C. Fettinger, Shigeru Nagase, et al.. "Dispersion Force Stabilized Two-coordinate Transition Metal-Amido Complexes of the -N(SiMe₃)Dipp (Dipp = C₆H₃-2,6-Pri₂) Ligand: Structural, Spectroscopic, Magnetic, and Computational Studies" Inorganic Chemistry Vol. 52 Iss. 23 (2013) p. 13584 - 13593 ISSN: 0020-1669
Available at: http://works.bepress.com/gary-long/145/