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Fliedel C, Rosa V, Vileno B, et al. Zwitterionic Cobalt Complexes with Bis(diphenylphosphino)(N-thioether)amine Assembling Ligands: Structural, EPR, Magnetic, and Computational Studies. Inorg Chem. 2016;55(9):4183-98doi: 10.1021/acs.inorgchem.5b02889.
Fliedel, C., Rosa, V., Vileno, B., Parizel, N., Choua, S., Gourlaouen, C., Rosa, P., Turek, P., & Braunstein, P. (2016). Zwitterionic Cobalt Complexes with Bis(diphenylphosphino)(N-thioether)amine Assembling Ligands: Structural, EPR, Magnetic, and Computational Studies. Inorganic chemistry, 55(9), 4183-98. https://doi.org/10.1021/acs.inorgchem.5b02889
Fliedel, Christophe, et al. "Zwitterionic Cobalt Complexes with Bis(diphenylphosphino)(N-thioether)amine Assembling Ligands: Structural, EPR, Magnetic, and Computational Studies." Inorganic chemistry vol. 55,9 (2016): 4183-98. doi: https://doi.org/10.1021/acs.inorgchem.5b02889
Fliedel C, Rosa V, Vileno B, Parizel N, Choua S, Gourlaouen C, Rosa P, Turek P, Braunstein P. Zwitterionic Cobalt Complexes with Bis(diphenylphosphino)(N-thioether)amine Assembling Ligands: Structural, EPR, Magnetic, and Computational Studies. Inorg Chem. 2016 May 02;55(9):4183-98. doi: 10.1021/acs.inorgchem.5b02889. Epub 2016 Apr 07. PMID: 27054464.
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Inorg Chem. 2016 May 02;55(9):4183-98. doi: 10.1021/acs.inorgchem.5b02889. Epub 2016 Apr 07.

Zwitterionic Cobalt Complexes with Bis(diphenylphosphino)(N-thioether)amine Assembling Ligands: Structural, EPR, Magnetic, and Computational Studies.

Inorganic chemistry

Christophe Fliedel, Vitor Rosa, Bertrand Vileno, Nathalie Parizel, Sylvie Choua, Christophe Gourlaouen, Patrick Rosa, Philippe Turek, Pierre Braunstein

Affiliations

  1. French EPR Federation of Research (REseau NAtional de Rpe interDisciplinaire, RENARD), Fédération IR-RPE CNRS 3443, 67081 Strasbourg, France.
  2. CNRS, Université de Bordeaux, ICMCB , UPR9048, F-33600 Pessac, France.

PMID: 27054464 DOI: 10.1021/acs.inorgchem.5b02889

Abstract

The coordination of two heterofunctional P,P,S ligands of the N-functionalized DPPA-type bearing an alkylthioether or arylthioether N-substituent, (Ph2P)2N(CH2)3SMe (1) and (Ph2P)2N(p-C6H4)SMe (2), respectively, toward cobalt dichloride was investigated to examine the influence of the linker between the PNP nitrogen and the S atoms. The complexes [CoCl2(1)]2 (3) and [CoCl2(2)]2 (4) have been isolated, and 3 was shown by X-ray diffraction to be a unique dinuclear, zwitterion containing one CoCl moiety bis-chelated by two ligands 1 and one CoCl3 fragment coordinated by the S atom of a thioether function. The FT-IR, UV-vis, and EPR spectroscopic features of 3 were analyzed as the superposition of those of constitutive fragments identified by a retrosynthetic-type analysis. A similar approach provided insight into the nature of 4 for which no X-ray diffraction data could be obtained. A comparison between the spectroscopic features of 4 and of its constitutive fragments, [CoCl(2)2]PF6 (7) and [H2']2[CoCl4] (8) (2' = NH2(p-C6H4)SMe), and between those of 4 and 3 suggested that 4 could either have a zwitterionic structure, similar to that of 3, or contain a tetrahedral dicationic bis-chelated Co center associated with a CoCl4 dianion. Magnetic and EPR studies and theoretical calculations were performed. Doublet spin states were found for the pentacoordinated complexes [CoCl(1)2]PF6 (5) and 7 and anisotropic quadruplet spin states for the tetrahedral complexes [CoCl3(H1')] (6) (1' = NH2(CH2)3SMe) and 8. A very similar behavior was observed for 3 and 4, consisting in the juxtaposition of noninteracting doublet and quadruplet spin states. Antiferromagnetic interactions explain the formation of dimers for 6 and of layers for 8. The EPR signatures of 3 and 4 correspond to the superposition of low-spin nuclei in 5 and 7 and high-spin nuclei in 6 and 8, respectively. From DFT calculations, the solid-state structure of 4 appears best described as zwitterionic, with a low-spin state for the Co1 atom.

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