English
 
Help Privacy Policy Disclaimer
  Advanced SearchBrowse

Item

ITEM ACTIONSEXPORT
  Carbodicarbene Ligand Redox Noninnocence in Highly Oxidized Chromium and Cobalt Complexes

Chan, S.-C., Ang, Z. Z., Gupta, P., Ganguly, R., Li, Y., Ye, S., et al. (2020). Carbodicarbene Ligand Redox Noninnocence in Highly Oxidized Chromium and Cobalt Complexes. Inorganic Chemistry, 59(6), 4118-4128. doi:10.1021/acs.inorgchem.0c00153.

Item is

Files

show Files

Locators

show

Creators

show
hide
 Creators:
Chan, Siu-Chung1, Author
Ang, Zhi Zhong1, Author
Gupta, Puneet2, Author           
Ganguly, Rakesh1, Author
Li, Yongxin1, Author
Ye, Shengfa2, 3, Author           
England, Jason1, Author
Affiliations:
1Division of Chemistry and Biological Chemistry, School of Physical and Mathematical Sciences, Nanyang Technological University (NTU), 21 Nanyang Link, 637371, Singapore, ou_persistent22              
2Research Group Ye, Max-Planck-Institut für Kohlenforschung, Max Planck Society, ou_2541708              
3State Key Laboratory of Catalysis, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023, China, ou_persistent22              

Content

show
hide
Free keywords: -
 Abstract: Carbodicarbenes (CDCs) possess two lone pairs of electrons on their central carbone C atom (Ccarbone). Coordination to a transition metal via a σ bond leaves one pair of electrons with appropriate symmetry for π donation to the metal. However, the high energy of the latter also renders the CDC ligand potentially redox-active. Herein, we explore these alternatives in the redox series [Cr(L)2]n+ and [Co(L)2]n+ (n = 2–5), where L is a tridentate ligand comprised of a central CDC and two flanking pyridine donors. To this end, all members of both redox series were synthesized and their electronic structures were investigated by using a combination of 1H NMR, Evans’ NMR, IR, UV–vis, and EPR spectroscopies, SQUID magnetometry, X-ray crystallography, and density functional theory studies. Whereas [CoII(L)2]2+ is a straightforward low-spin (S = 1/2) cobalt(II) complex, the corresponding chromium complex was found to feature an electronic structure that is intermediate between the two limiting resonance forms [CrIII(L•–)(L)]2+ and [CrII(L)2]2+. In the case of the tri-, tetra-, and pentacationic complexes, the qualitatively identical electronic structures [MIII(L)2]3+, [MIII(L•+)(L)]4+, and [MIII(L•+)2]5+ were observed for both metals. Thus, the metal ions retain a 3+ oxidation state throughout, and the higher redox states contain oxidized ligands. The majority of the unpaired spin on the cation radical ligands was calculated to be localized in π-symmetry orbitals on the coordinated Ccarbone atoms. Analogous behavior was previously reported for the corresponding iron redox series and, as such, redox noninnocence in oxidized CDC and, more broadly, carbone complexes is likely widely accessible.

Details

show
hide
Language(s): eng - English
 Dates: 2020-01-162020-02-262020-03-16
 Publication Status: Published in print
 Pages: 11
 Publishing info: -
 Table of Contents: -
 Rev. Type: Peer
 Identifiers: DOI: 10.1021/acs.inorgchem.0c00153
 Degree: -

Event

show

Legal Case

show

Project information

show

Source 1

show
hide
Title: Inorganic Chemistry
  Abbreviation : Inorg. Chem.
Source Genre: Journal
 Creator(s):
Affiliations:
Publ. Info: Washington, DC : American Chemical Society
Pages: - Volume / Issue: 59 (6) Sequence Number: - Start / End Page: 4118 - 4128 Identifier: ISSN: 0020-1669
CoNE: https://pure.mpg.de/cone/journals/resource/0020-1669