Synthesis, Characterization and X-Ray Crystal Structure of a Cobalt(III) Complex with 2-Bis(pyridine-2-carboxamido)-4,5-dimethylbenzene Ligand

Document Type : Research Paper

Authors

1 Isfahan University of Technology

2 Vienna University of Technology, Austria

3 Department of Chemistry, University of Tehran

Abstract

An octahedral cobalt(III) complex, trans-[(Me2bpb)Co(bzlan)2]ClO4 (1), with H2Me2bpb = N,N’-(4,5-dimethyl-1,2-phenylene)dipicolinamide and bzlan = benzylamine, has been synthesized and characterized by elemental analyses, IR, UV-Vis, and 1H NMR spectroscopy. The structure of this complex has been determined by X-ray crystallography. The Me2bpb2– is a di-anionic tetradentate ligand furnishing a N4 set, such that two N atoms of the two pyridine rings and two amido N atoms occupy four equatorial positions. The two benzylamine ligands occupy the two axial positions leading to a distorted octahedral geometry around the central cobalt ion. The electrochemical behavior of this complex in acetonitrile solution indicates that the irreversible oxidation of 4,5-dimethylorthophenylene moiety and reduction of pyridine rings of the free ligand appear as reversible waves in the cyclic voltammogram of its cobalt(III) complex. Concomitant CoIII/CoII redox process and solvolysis in acetonitrile solution is observed. This irreversible redox process becomes reversible in the presence of excess benzylamine.

Keywords


[1] T.C. Harrop, M.M. Olmstead, P.K. Mascharak, Inorg.
Chem. 44 (2005) 9527.
[2] A.K. Singh, R. Mukherjee, Inorg. Chem. 44 (2005)
5813.
[3] P.K. Mascharak, Coord. Chem. Rev. 225 (2002) 201.
[4] T.C. Harrop, P.K. Mascharak, Acc. Chem. Res. 37
(2004) 253.
[5] A. Mohamadou, J.-P. Barbier, J. Marrot, Inorg. Chim.
Acta 360 (2007) 2485.
[6] D.S. Auld, T. Bergman, Cell. Mol. Life Sci. 65 (2008)
3961.
[7] E.N. Salgado, J.D. Brodin, M.M. To, F.A. Tezcan,
Inorg. Chem. 50 (2011) 6323.
[8] M.L. Zastrow, A.F.A. Peacock, J.A. Stuckey, V.L.
Pecoraro, Nature Chem. 4 (2012) 118.
[9] M.J. Wiester, P.A. Ulmann, C.A. Mirkin, Angew.
Chem. Int. Ed. 50 (2011) 114.
[10] Q. Zhu, X. Wang, Z. Chu, G. He, G. Dong, Y. Xu,
Bioorg. Med. Chem. Lett. 23 (2013) 1993.
[11] L. Yang, R.L. Wei, R. Li, X.G. Zhou, J.L. Zuo, J.
Mol. Catal. A: Chem. 266 (2007) 284.
[12] D.H. Lee, J.Y. Lee, J.Y. Ryu, Y. Kim, C. Kim, I.-M.
Lee, Bull. Korean Chem. Soc. 27 (2006) 1031.
[13] R. Ramachandran, P. Viswanathamurthi,
Spectrochim. Acta Part A 103 (2013) 53.
[14] B.-W. Lee, K.S. Min, M.-K. Doh, Inorg. Chem.
Commun. 5 (2002) 163.
[15] W. Jacob, R. Mukherjee, Inorg. Chim. Acta 361
(2008) 1231.
[16] L. Zhang, X. Huang, D.E. Kang, C.-S. Ha, H. Suh, I.
Kim, Supramolecular Chem. 24 (2012) 165.
[17] H. Adolfsson, C. Moberg, Tetrahedron: Asym. 6
(1995) 2023.
[18] S. Meghdadi, K. Mereiter, A. Amiri, N.S.
Mohammadi, F. Zamani, M. Amirnasr, Polyhedron 29
(2010) 2225.
[19] S. Meghdadi, M. Amirnasr, M.H. Habibi, A. Amiri,
V. Ghodsi, A. Rohani, R.W. Harrington, W. Clegg,
Polyhedron 27 (2008) 2771.
[20] S. Meghdadi, V. Mirkhani, R. Kia, M. Moghadam, S.
Tangestaninejad, I. Mohammadpoor-Baltork,
Polyhedron 41 (2012) 115.
[21] S. Meghdadi, M. Amirnasr, S.B.H. Moein Sadat, K.
Mereiter, A. Amiri, Monatsh. Chem. 145 (2014) 1583
[22] S. Meghdadi, M. Amirnasr, A. Amiri, Z. Musavizadeh
Mobarakeh, Z. Azarkamanzad, C. R. Chim. 17 (2014)
477.
[23] N.G. Connelly, W.E. Geiger, Chem. Rev. 96 (1996)
877.
[24] Bruker Computer Programs: APEX2, Version 2008;
SAINT, Version 7.68A; SADABS, Version 2008/1;
SHELXTL, Version 2008/4. Bruker AXS Inc.,
Madison, WI, 2008.
[25] G.M. Sheldrick, SHELX97, Acta Crystallogr., Sect. E
64 (2008) 112.
[26] S.K. Dutta, U. Beckmann, E. Bill, T. Weyhermuller,
K. Wieghardt, Inorg. Chem. 39 (2000) 3355.
[27] S. Meghdadi, K. Mereiter, M. Amirnasr, F. Karimi, A.
Amiri, Polyhedron 68 (2014) 60.
[28] F.S. Stephens, R.S. Vagg, Inorg. Chim. Acta 120
(1986) 165.
[29] S.K. Dutta, U. Beckmann, E. Bill, T. Weyhermüller,
K. Wieghardt, Inorg. Chem. 39 (2000) 3355.
[30] C.L. Weeks, P. Turner, R.R. Fenton, P.A. Lay, J.
Chem. Soc., Dalton Trans. (2002) 931.