Iron and Nickel -ligand bonding in metallocene: Differentiation between bond Stability and reactivity
( Vol-4,Issue-7,July 2017 )

Tesfalem Belay Woldeamanuale


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


The electronic structure and geometry optimization of ferrocene and nickelocene molecules are calculated using DFT/B3LYP with the basis set of 6-31G (d).The Eigen values, Eigen vector and population analysis of the molecules show that thefirst 13 molecular orbitals in ferrocene and 14 in nickelocene have contribution from 2pzorbitals of carbon of (C5H5) – and 4s, 4pand 3dorbitals of iron andnickel respectively. We found that the extent of involvement of metal orbitals in thetwo cases is different. In ferrocene the maximum involvement out of 4sand 4porbital is 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 innickelocene with respect to the 4sand 4porbitals is in the order of 4py> 4px> 4s> 4pz and in 3d orbitals the order is 3dyz >3dx2-y2 >3dxy >3dxz >3dz2molecules. The total involvement of 3d, 4s and 4porbitals of metal and 2pz orbitals of the ten carbon atomsof both ligands of (C5H5) −in ferrocene and nickelocene respectively are 42.2528 and 38.3776 hence we can conclude that ferrocene is more stable than nickelocene. Similar results are found from calculation of parameters like dipole moment, HOMO-LUMO gap and Mullikan charge distribution. The population analysis shows that only 2pz orbitals of carbon of (C5H5) −and 3d orbitals of metal provide electrons to MOs of ferrocene and nickelocene.

ijaers doi crossref DOI:


Paper Statistics:
  • Total View : 349
  • Downloads : 31
  • Page No: 006-019
Cite this Article:
Show All (MLA | APA | Chicago | Harvard | IEEE | Bibtex)

[1] FA Cotton, G Wilkinson, PL Gaus. Basic Inorganic Chemistry, 3rd ed., Wiley and Sons, Asia, 2001, pp 667.
[2] S Girolami, 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, 5th edn., 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. S.Complexes of Cobaltocene: and Effective 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 Nickelocene, 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).