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International Journal Of Chemistry, Mathematics And Physics(IJCMP)

Iron, cobalt and Nickel -ligand bonding in metallocene: Differentiation between bonds Stability and reactivity

Tesfalem Belay Woldeamanuale

International Journal of Chemistry, Mathematics And Physics(IJCMP), Vol-1,Issue-2, July - August 2017, Pages 1-19 ,

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The electronic structure and geometry optimization of ferrocene, cobaltocene and nickelocene molecules using DFT/B3LYP with the basis set of 6-31G (d) calculations. The Eigen values, Eigen vector and population analysis of the molecules show that the first 13 molecular orbitals in ferrocene, 12 in cobaltocene and 14 in nickelocene have contribution from 2pzorbitals of carbon of (C5H5)− and4s,4pand 3dorbitals of iron, cobalt or nickel, respectively. We found that the extents of involvement of metal orbitals in the three cases are different. In ferrocene the maximum involvement out of 4s and 4porbitals in the order 4pz >4py >4s > 4pxand out of 3d orbitals the order of involvement is 3dyz >3dxz >3d2z>3dx2−y2>3dxy. The involvement of corresponding orbital in cobaltocene with respect to the 4sand 4porbitals is in the order of 4s >4pz >4py >4pxand in 3d orbitals the order is 3dx2−y2>3dxz >3d2z>3dx2−y2 and in the nickelocene molecule it is 4py >4p>4s >4pz and in 3d orbitals the order is 3dyz >3dx2−y2>3dxy >3dxz >3d2z. The total involvement of 3d, 4s and 4porbitals of metal and 2pz orbitals of the ten carbon atoms of both ligands of (C5H5) −in ferrocene, cobaltocene and nickelocene respectively are 42.2528, 40.2388 and 38.3776

Ferrocene, Cobaltocene, Nickelocene, Eigen vector, population analysis, Eigenvalues, atomic and molecular orbitals.

[1] FA Cotton, G Wilkinson, PL Gaus. Basic Inorganic Chemistry, 3rd ed., Wiley and Sons, Asia, 2001, pp 667.
[2] SGirolami, TB Rauchfuss, RJ Angelici. Synthesis and Technique in Inorganic Chemistry, CA: University Science Books- Mill Valley, 1999.
[3] ER Davidson. Chem. Rev. 2000, 100, 351.
[4] ER Davidson. Chem. Rev. 1991, 91, 649.
[5] RF Nalewajski. Topics in current chemistry, Ed., Heidelberg: Berlin: Springer-Verlag, 1996, pp 180.
[6] RG Parr, W Yang. Density Functional Theory of atoms and molecules, Eds., New York: Oxford University Press, 1989.
[7] J Labanowski, J and elm. Density Functional Methods in Chemistry, Eds., Heidelberg: Springer-Verlag, 1991.
[8] T Ziegler, Chem. Rev. 1991, 91, 651.
[9] L Szasz. Pseudopotential Theory of Atoms and Molecules, New York: J. Wiley & Sons, 1986.
[10] M Krauss; WJ Stevens. Ann. Rev. Phys. Chem. 1984, 35, 357.
[11] P Durand; JP Malrieu, Adv. Chem. Phys. 1987, 67, 321.
[12] TR Cundari, MT Benson, ML Lutj, SO Sommerer, Reviews in Computational Chemistry, KB Lipkowitz, DB Boyd, Eds.; VCH: New York, 1996, 8, pp145.
[13] RC Mehrotra, A Singh. Organometallic Chemistry, Wiley Eastern Ltd. 1992, pp 247.
[14] IN Levine Quantum Chemistry, 5thedn. New Jersey: Prentice Hall, 2000, pp 664.
[15] DA Cleary; AH Francis, J. Phys. Chem. 1985, 89, pp 97.
[16] PK Byszewski; E Antonova; J Kowalska; Radomska; J Baran, Chem. Phys. Lett. 2000, 323, pp 522.
[17] C Elschenbroich, ASalzer. Organometallics, VCH: Weinheim, 1991.
[18] G Wilkinson; PL Pauson, FA Cotton, J Am. Chem. Soc. 1954, 76, pp 1970.
[19] JH Schachtschneider; R Prins; P Ros, Inorg.Chim. Act. 1967, 1, pp 462.
[20] ER David. Chem. Rev. 2000, 100, pp 351
[21] G. K.; Ra, N. V. and P. P. S.Molecular mechanics and Quantum Chemistry Study ofCobaltocene and Nickelocene, Archives of Physics Research, Vol.3, No. 2, PP. 297-310,2011.
[22] V. Kahn. S. G. Kahn., R. N. V. and Pashupati .P. Complexes of Cobaltocene: anEffective Atomic Softness and Fukui Function Based Study, Journal of Pharmaceutical, Biological and Chemical Sciences, Vol.5, No. 12, PP. 211-326, 2010.
[23] Khan. Molecular Mechanics Based Study on Molecular and Atomic Orbital of Nick-elocene, Journal of Applied Chemical Research, Vol.10, No. 19, PP.66-84, 2011.
[24] G. Kahn. And Rajendra, P. T.Study of MolecularOrbitals of Ruthenium (II) Bromide Based on Molecular Mechanics, K. S. Saket Post Graduate College, Ayodhya, Faizabad, U. P. INDIA, Applied Science Research, Vol.3, No. 2, pp. 483-492, 2011.
[25] G. Kahn. Comparative Study of Molecular Orbitals of Cobaltocene and Nickelocene Based on Molecular Mechanics, K. S. Saket Post Graduate College, Ayodhya, Faizabad, U. P. INDIA, Applied Science Research, Vol.3, No. 2, pp. 297-310, 2011.
[26] P. P. Singh, P. Mishra and J. P. Singh. Molecular mechanics and quantum chemistry based study of cobalt-thiazolidinedione complexes, Bareilly College, Bareilly, U.P.Vol.34, No. 3, pp. 215-224,(2006).