Synthesis, thermal studies and spectral characterization of Co(II), Ni(II), Cu(II), and Zn(II) complexes with some polymeric diacetyl acyldihydrazone ligands

Vinod Prasad Singh; Divya Pratap Singh

Macromolecular Research, Vol.21, No.7, 757-766, July, 2013

DOI10.1007/s13233-013-1084-8 Export Citation

Synthesis, thermal studies and spectral characterization of Co(II), Ni(II), Cu(II), and Zn(II) complexes with some polymeric diacetyl acyldihydrazone ligands

Vinod Prasad Singh^†, and Divya Pratap Singh

Department of Chemistry, Banaras Hindu University, Varanasi, 221005, India

E-mail:

Two polymeric ligands, diacetyl oxaloyldihydrazone (DODH), diacetyl malonoylhydrazone (DMDH) and their Co(II), Ni(II), Cu(II) and Zn(II) complexes were synthesized and characterized by elemental analyses, IR, mass, 1H & 13C NMR, ESR and electronic spectral studies. The ligands and their complexes are highly insoluble in water and common organic solvents and decompose at high temperature. The metal atoms are embedded between two polymeric chains of the organic ligands and the monomeric unit of the polymeric chain behaves as a neutral bidentate ligand and coordinate through two >C=N groups to different metals as indicated by 1H & 13C NMR and IR spectral studies. The molecular weights determined by 1H NMR and mass spectral studies suggest oligomeric nature of the ligands and their Zn(II) complexes. The magnetic susceptibility measurements and electronic spectral studies indicate a square planar geometry around the metal ion in Co(II) and Ni(II) complexes. Electronic and ESR spectral studies for Cu(II) complexes suggest a distorted octahedral stereochemistry around the metal atom and 2B1g as the ground state. Thermal studies (TGA and DTA) of some of the complexes in inert atmosphere show a multi-step exothermic decomposition of the bonded organic ligand at high temperature and metal (II) chloride as the end product.

Keywords:polymeric metal complexes;acyldihydrazones;thermal studies;NMR spectra;ESR spectra;mass spectrometry

[References]

Stevens MP, in Polymer Chemistry: An Introduction, 2nd ed., Oxford University, London, 1990, pp 487-508.
Seymour RB, Carraher CE, in Polymer Chemistry: An Introduction, 3rd ed., Marcel & Dekker, 1992, pp 381-401.
Mark JE, Allcock HR, West R, in Inorganic Polymers, Prentice-Hall, 1992, pp 141-185.
Janiak C, J. Chem. Soc.-Dalton Trans., 2781 (2003)
Uemura K, Matsuda R, Kitagawa S, J. Solid State Chem., 178, 2420 (2005)
Kesanli B, Lin W, Coord. Chem. Rev., 246, 305 (2003)
Batten SR, Murray KS, Coord. Chem. Rev., 246, 103 (2003)
Abd-El-Aziz AS, Shipman PO, Boden BN, McNeil WS, Prog. Polym. Sci, 35, 714 (2010)
Robin AY, Fromm KM, Coord. Chem. Rev., 250, 2127 (2006)
Kaliyappan T, Murugavel SC, Kannan P, Polym. Int., 45, 278 (1999)
Marcu M, Cazacu M, Vlad A, Racles C, Appl. Organomet. Chem., 17, 693 (2003)
Singh VP, Singh A, Singh S, J. Appl. Polym. Sci., 110(3), 1336 (2008)
Singh VP, Katiyar A, Singh S, Biomaterials, 21, 491 (2008)
Singh VP, Singh S, Katiyar A, J. Enzyme Inhib. Med. Chem., 24, 577 (2009)
Singh VP, Gupta P, J. Enzyme Inhib. Med. Chem., 23, 797 (2008)
Singh VP, Gupta P, J. Coord. Chem., 61, 3922 (2008)
Vogel AI, Vogel’s Textbook of Quantitative Chemical Analyses, 5th ed., Longman, Amsterdam, 1989.
Geary WJ, Coord. Chem. Rev., 7, 81 (1971)
Lever ABP, Inorganic Electronic Spectroscopy, 2nd ed., Elsevier, Amsterdam, 1984.
Bigoli F, Cassoux P, Deplano P, Mercuri ML, Pellinghelli MA, Pintus G, Serpe A, Trogu EF, J. Chem. Soc.-Dalton Trans., 24, 4639 (2000)
Dutta RL, Syamal A, Elements of Magnetochemistry, Affiliated East-West Press Pvt. Ltd., New Delhi, 1993.
Cotton FA, Wilkinson G, Murillo CA, Bachmann M, Advanced Inorganic Chemistry, 6th ed., Wiley, New York, 2003.
Hathaway BJ, Billing DE, Coord. Chem. Rev., 5, 143 (1970)
Singh OI, Damayanti B, Singh NR, Singh RKH, Mohapatra M, Kadam RM, Polyhedron, 24, 909 (2005)
Bindu P, Kurup MRP, Satyakeerty TR, Polyhedron, 18, 321 (1999)
Silverstein RM, Webster FX, Kiemle D, Spectrometric Identification of Organic Compounds, 7th ed., Wiley, New York, 2005.
Singh B, Srivastav AK, Synth. React. Inorg. Met.-Org. Chem., 21, 513 (1991)
Singh B, Srivastav AK, Transion Met. Chem., 14, 415 (1989)
Mishra AK, Patel VK, Vishwakarma NK, Biswas CS, Raula M, Misra A, Mandal TK, Ray B, Macromolecules, 44(8), 2465 (2011)
Nakamoto K, Infrared and Ramam Spectra of Inorganic and Coordination Compounds, 4th ed., Wiley Interscience, New York, 1993.
Singh VP, Spectroc. Acta Pt. A-Molec. Biomolec. Spectr., 71, 17 (2008)

[Referenced By]

[1] Stevens MP, in Polymer Chemistry: An Introduction, 2nd ed., Oxford University, London, 1990, pp 487-508.

[2] Seymour RB, Carraher CE, in Polymer Chemistry: An Introduction, 3rd ed., Marcel & Dekker, 1992, pp 381-401.

[3] Mark JE, Allcock HR, West R, in Inorganic Polymers, Prentice-Hall, 1992, pp 141-185.

[4] Janiak C, J. Chem. Soc.-Dalton Trans., 2781 (2003)

[5] Uemura K, Matsuda R, Kitagawa S, J. Solid State Chem., 178, 2420 (2005)

[6] Kesanli B, Lin W, Coord. Chem. Rev., 246, 305 (2003)

[7] Batten SR, Murray KS, Coord. Chem. Rev., 246, 103 (2003)

[8] Abd-El-Aziz AS, Shipman PO, Boden BN, McNeil WS, Prog. Polym. Sci, 35, 714 (2010)

[9] Robin AY, Fromm KM, Coord. Chem. Rev., 250, 2127 (2006)

[10] Kaliyappan T, Murugavel SC, Kannan P, Polym. Int., 45, 278 (1999)

[11] Marcu M, Cazacu M, Vlad A, Racles C, Appl. Organomet. Chem., 17, 693 (2003)

[12] Singh VP, Singh A, Singh S, J. Appl. Polym. Sci., 110(3), 1336 (2008)

[13] Singh VP, Katiyar A, Singh S, Biomaterials, 21, 491 (2008)

[14] Singh VP, Singh S, Katiyar A, J. Enzyme Inhib. Med. Chem., 24, 577 (2009)

[15] Singh VP, Gupta P, J. Enzyme Inhib. Med. Chem., 23, 797 (2008)

[16] Singh VP, Gupta P, J. Coord. Chem., 61, 3922 (2008)

[17] Vogel AI, Vogel’s Textbook of Quantitative Chemical Analyses, 5th ed., Longman, Amsterdam, 1989.

[18] Geary WJ, Coord. Chem. Rev., 7, 81 (1971)

[19] Lever ABP, Inorganic Electronic Spectroscopy, 2nd ed., Elsevier, Amsterdam, 1984.

[20] Bigoli F, Cassoux P, Deplano P, Mercuri ML, Pellinghelli MA, Pintus G, Serpe A, Trogu EF, J. Chem. Soc.-Dalton Trans., 24, 4639 (2000)

[21] Dutta RL, Syamal A, Elements of Magnetochemistry, Affiliated East-West Press Pvt. Ltd., New Delhi, 1993.

[22] Cotton FA, Wilkinson G, Murillo CA, Bachmann M, Advanced Inorganic Chemistry, 6th ed., Wiley, New York, 2003.

[23] Hathaway BJ, Billing DE, Coord. Chem. Rev., 5, 143 (1970)

[24] Singh OI, Damayanti B, Singh NR, Singh RKH, Mohapatra M, Kadam RM, Polyhedron, 24, 909 (2005)

[25] Bindu P, Kurup MRP, Satyakeerty TR, Polyhedron, 18, 321 (1999)

[26] Silverstein RM, Webster FX, Kiemle D, Spectrometric Identification of Organic Compounds, 7th ed., Wiley, New York, 2005.

[27] Singh B, Srivastav AK, Synth. React. Inorg. Met.-Org. Chem., 21, 513 (1991)

[28] Singh B, Srivastav AK, Transion Met. Chem., 14, 415 (1989)

[29] Mishra AK, Patel VK, Vishwakarma NK, Biswas CS, Raula M, Misra A, Mandal TK, Ray B, Macromolecules, 44(8), 2465 (2011)

[30] Nakamoto K, Infrared and Ramam Spectra of Inorganic and Coordination Compounds, 4th ed., Wiley Interscience, New York, 1993.

[31] Singh VP, Spectroc. Acta Pt. A-Molec. Biomolec. Spectr., 71, 17 (2008)