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On the Analysis of the Cr-Cr Multiple Bond in Several Classes of Dichromium Compounds

La Macchia, G.; Manni, G. Li; Todorova, T. K.; Brynda, M.; Aquilante, F.; Roos, Björn LU and Gagliardi, L. (2010) In Inorganic Chemistry 49(11). p.5216-5222
Abstract
Since the discovery of a formal quintuple bond in Ar'CrCrAr' (CrCr = 1.835 angstrom) by Power and co-workers in 2005, many efforts have been dedicated to isolating dichromium species featuring quintuple-bond character. In the present study we investigate the electronic configuration of several, recently synthesized dichromium species with ligands using nitrogen to coordinate the metal centers. The bimetallic bond distances of Power's compound and Cr-2-diazadiene (1) (CrCr = 1.803 angstrom) are compared to those found for Cr-2(mu-eta(2)-ArNC(R)NAr)(2) (2) (CrCr = 1.746 angstrom; R = H, Ar = 2,6-Et2C6H3), Cr-2(mu-eta(2)-(ArNC)-N-Xyl(H)NArXyl)(3) (3) (CrCr = 1.740(reduced)/1.817(neutral) angstrom; Ar-Xyl=2,6-C6H3-(CH3)(2)),... (More)
Since the discovery of a formal quintuple bond in Ar'CrCrAr' (CrCr = 1.835 angstrom) by Power and co-workers in 2005, many efforts have been dedicated to isolating dichromium species featuring quintuple-bond character. In the present study we investigate the electronic configuration of several, recently synthesized dichromium species with ligands using nitrogen to coordinate the metal centers. The bimetallic bond distances of Power's compound and Cr-2-diazadiene (1) (CrCr = 1.803 angstrom) are compared to those found for Cr-2(mu-eta(2)-ArNC(R)NAr)(2) (2) (CrCr = 1.746 angstrom; R = H, Ar = 2,6-Et2C6H3), Cr-2(mu-eta(2)-(ArNC)-N-Xyl(H)NArXyl)(3) (3) (CrCr = 1.740(reduced)/1.817(neutral) angstrom; Ar-Xyl=2,6-C6H3-(CH3)(2)), Cr-2(mu-eta(2)-TippPyNMes)(2) (4) (CrCr = 1.749 angstrom; TippPyNMes = 6-(2,4,6-triisopropylphenyl)pyridin-2-yl (2,4,6-trimethylphenyl)-amide), and Cr-2(mu-eta(2)-DippNC(NMe2)N-Dipp)(2) (5) (CrCr = 1.729 angstrom, Dipp = 2,6-i-Pr2C6H3). We show that the correlation between the CrCr bond length and the effective bond order (EBO) is strongly affected by the nature of the ligand, as well as by the steric hindrance due to the ligand structure (e.g., the nature of the coordinating nitrogen). A linear correlation between the EBO and CrCr bond distance is established within the same group of ligands. As a result, the CrCr species based on the amidinate, aminopyridinate, and guanidinate ligands have bond patterns similar to the Ar'CrCrAr' compound. Unlike these latter species, the dichromium diazadiene complex is characterized by a different bonding pattern involving Cr-N pi interactions, resulting in a lower bond order associated with the short metal-metal bond distance. In this case the short CrCr distance is most probably the result of the constraints imposed by the diazadiene ligand, implying a Cr2N4 core with a closer CrCr interaction. (Less)
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organization
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Contribution to journal
publication status
published
subject
in
Inorganic Chemistry
volume
49
issue
11
pages
5216 - 5222
publisher
The American Chemical Society
external identifiers
  • wos:000278110100067
  • scopus:77953058084
ISSN
1520-510X
DOI
10.1021/ic100345b
language
English
LU publication?
yes
id
9dfa6318-859d-4a4d-a5fb-e4bbf000b398 (old id 1616770)
date added to LUP
2010-06-22 13:39:50
date last changed
2018-05-29 11:50:35
@article{9dfa6318-859d-4a4d-a5fb-e4bbf000b398,
  abstract     = {Since the discovery of a formal quintuple bond in Ar'CrCrAr' (CrCr = 1.835 angstrom) by Power and co-workers in 2005, many efforts have been dedicated to isolating dichromium species featuring quintuple-bond character. In the present study we investigate the electronic configuration of several, recently synthesized dichromium species with ligands using nitrogen to coordinate the metal centers. The bimetallic bond distances of Power's compound and Cr-2-diazadiene (1) (CrCr = 1.803 angstrom) are compared to those found for Cr-2(mu-eta(2)-ArNC(R)NAr)(2) (2) (CrCr = 1.746 angstrom; R = H, Ar = 2,6-Et2C6H3), Cr-2(mu-eta(2)-(ArNC)-N-Xyl(H)NArXyl)(3) (3) (CrCr = 1.740(reduced)/1.817(neutral) angstrom; Ar-Xyl=2,6-C6H3-(CH3)(2)), Cr-2(mu-eta(2)-TippPyNMes)(2) (4) (CrCr = 1.749 angstrom; TippPyNMes = 6-(2,4,6-triisopropylphenyl)pyridin-2-yl (2,4,6-trimethylphenyl)-amide), and Cr-2(mu-eta(2)-DippNC(NMe2)N-Dipp)(2) (5) (CrCr = 1.729 angstrom, Dipp = 2,6-i-Pr2C6H3). We show that the correlation between the CrCr bond length and the effective bond order (EBO) is strongly affected by the nature of the ligand, as well as by the steric hindrance due to the ligand structure (e.g., the nature of the coordinating nitrogen). A linear correlation between the EBO and CrCr bond distance is established within the same group of ligands. As a result, the CrCr species based on the amidinate, aminopyridinate, and guanidinate ligands have bond patterns similar to the Ar'CrCrAr' compound. Unlike these latter species, the dichromium diazadiene complex is characterized by a different bonding pattern involving Cr-N pi interactions, resulting in a lower bond order associated with the short metal-metal bond distance. In this case the short CrCr distance is most probably the result of the constraints imposed by the diazadiene ligand, implying a Cr2N4 core with a closer CrCr interaction.},
  author       = {La Macchia, G. and Manni, G. Li and Todorova, T. K. and Brynda, M. and Aquilante, F. and Roos, Björn and Gagliardi, L.},
  issn         = {1520-510X},
  language     = {eng},
  number       = {11},
  pages        = {5216--5222},
  publisher    = {The American Chemical Society},
  series       = {Inorganic Chemistry},
  title        = {On the Analysis of the Cr-Cr Multiple Bond in Several Classes of Dichromium Compounds},
  url          = {http://dx.doi.org/10.1021/ic100345b},
  volume       = {49},
  year         = {2010},
}