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

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 1–3 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.

International Standard Serial Number (ISSN)

0020-1669

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

01 Dec 2013

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