3d Metal Complexes Supported by a Bis(imidazolin-2-imino)pyridine Pincer Ligand - Synthesis, Structural Characterisation, and Magnetic Properties

Filimon S-A, Petrovic D, Volbeda J, Bannenberg T, Jones PG, von Richthofen C-G, Glaser T, Tamm M (2014)
Eur. J. Inorg. Chem. (35): 5997-6012.

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Abstract
The coordination chemistry of the tridentate pincer ligand TLtBu, which contains two electron-rich imidazolin-2-imine moieties, has been explored. The reaction of TLtBu with metal dihalides gave complexes of the general formula [(TLtBu)-MX2] (M = Mn, Fe, Co, Ni; X = Cl, Br). These complexes were characterized by X-ray diffraction analysis, which showed them to have different geometries in the solid state. Although [(TLtBu) MnCl2] (1) is best described as distorted square-pyramidal, the complexes [(TLtBu) FeCl2] (2) and [(TLtBu) CoCl2] (3) show distorted tetrahedral geometries with the TLtBu ligand bound in a kappa(2) fashion and one of its imidazolin- 2-imine fragments not coordinated to the metal atom. [(TLtBu) NiBr]Br (4) crystallizes with a slightly distorted square-planar cation. The reaction of the triflate (OTf) salts [M(OTf)(2)center dot nMeCN] (M = Mn, n = 1; M = Fe, Co, n = 2; OTf = CF3SO3) with TLtBu resulted in [(TLtBu) M(OTf)][OTf] (M = Mn, 5; M = Fe, 6) and [(TLtBu) Co(NCMe)][OTf](2) (7). Complexes 6 and 7 were characterized by X-ray diffraction analysis, and both showed distorted square-planar geometries. Magnetic measurements of 5, 6 and 7 showed them to possess a S = 5/2, 2 and 1/2 ground states, respectively. The bromide ions in complex 4 were exchanged by reaction with AgBF4 to afford [(TLtBu) Ni(NCMe)][BF4](2) (8), which showed a distorted square-planar geometry in the solid state. The reactions of 1 and 6 with AgOTf resulted in the oxidation of the complexes and the formation of [(TLtBu)MnCl(OTf)][OTf] (9) and [(TLtBu) Fe(OTf)(2)][OTf] (10), respectively. Complexes 9 and 10 both display distorted square-pyramidal geometries in the solid state. The ground state of 10 was found to be S = 5/2 by superconducting quantum interference device (SQUID) magnetometry measurements. The oxidation of 5, 6 and 7 with the iodosobenzene derivative ((SO2)-S-tBu)C6H4IO was investigated. Although the reactions of 6 and 7 gave no evidence for the formation of transient oxo species, crystals were obtained from the reaction of 5. These crystals showed the formation of [TLtBu*Mn(OH)]-(OTf)(2) (11), in which one of the tBu groups of the TLtBu ligand has undergone a C-H activation by a putative Mn-IV= O bond. The complex shows a distorted square-pyramidal geometry in the solid state, and the carbon atom of the CH-activated tBu group occupies the apical position.
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Filimon S-A, Petrovic D, Volbeda J, et al. 3d Metal Complexes Supported by a Bis(imidazolin-2-imino)pyridine Pincer Ligand - Synthesis, Structural Characterisation, and Magnetic Properties. Eur. J. Inorg. Chem. 2014;(35):5997-6012.
Filimon, S. - A., Petrovic, D., Volbeda, J., Bannenberg, T., Jones, P. G., von Richthofen, C. - G., Glaser, T., et al. (2014). 3d Metal Complexes Supported by a Bis(imidazolin-2-imino)pyridine Pincer Ligand - Synthesis, Structural Characterisation, and Magnetic Properties. Eur. J. Inorg. Chem.(35), 5997-6012.
Filimon, S. - A., Petrovic, D., Volbeda, J., Bannenberg, T., Jones, P. G., von Richthofen, C. - G., Glaser, T., and Tamm, M. (2014). 3d Metal Complexes Supported by a Bis(imidazolin-2-imino)pyridine Pincer Ligand - Synthesis, Structural Characterisation, and Magnetic Properties. Eur. J. Inorg. Chem., 5997-6012.
Filimon, S.-A., et al., 2014. 3d Metal Complexes Supported by a Bis(imidazolin-2-imino)pyridine Pincer Ligand - Synthesis, Structural Characterisation, and Magnetic Properties. Eur. J. Inorg. Chem., (35), p 5997-6012.
S.-A. Filimon, et al., “3d Metal Complexes Supported by a Bis(imidazolin-2-imino)pyridine Pincer Ligand - Synthesis, Structural Characterisation, and Magnetic Properties”, Eur. J. Inorg. Chem., 2014, pp. 5997-6012.
Filimon, S.-A., Petrovic, D., Volbeda, J., Bannenberg, T., Jones, P.G., von Richthofen, C.-G., Glaser, T., Tamm, M.: 3d Metal Complexes Supported by a Bis(imidazolin-2-imino)pyridine Pincer Ligand - Synthesis, Structural Characterisation, and Magnetic Properties. Eur. J. Inorg. Chem. 5997-6012 (2014).
Filimon, Sabina-Alexandra, Petrovic, Dejan, Volbeda, Jeroen, Bannenberg, Thomas, Jones, Peter G., von Richthofen, Carl-Georg, Glaser, Thorsten, and Tamm, Matthias. “3d Metal Complexes Supported by a Bis(imidazolin-2-imino)pyridine Pincer Ligand - Synthesis, Structural Characterisation, and Magnetic Properties”. Eur. J. Inorg. Chem. 35 (2014): 5997-6012.
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