Document Detail

Density functional investigation and bonding analysis of pentacoordinated iron complexes with mixed cyano and carbonyl ligands.
MedLine Citation:
PMID:  20087908     Owner:  NLM     Status:  MEDLINE    
The equilibrium structures and vibrational frequencies of the iron complexes [Fe(0)(CN)(n)(CO)(5-n)](n-) and [Fe(II)(CN)(n)(CO)(5-n)](2-n) (n = 0-5) have been calculated at the BP86 level of theory. The Fe(0) complexes adopt trigonal bipyramidal structures with the cyano ligands occupying the axial positions, whereas corresponding Fe(2+) complexes adopt square pyramidal structures with the cyano ligands in the equatorial positions. The calculated geometries and vibrational frequencies of the mixed iron Fe(0) carbonyl cyanide complexes are in a very good agreement with the available experimental data. The nature of the Fe-CN and Fe-CO bonds has been analyzed with both charge decomposition and energy partitioning analysis. The results of energy partitioning analysis of the Fe-CO bonds shows that the binding interactions in Fe(0) complexes have 50-55% electrostatic and 45-50% covalent character, whereas in Fe(2+) 45-50% electrostatic and 50-55% covalent character. There is a significant contribution of the pi- orbital interaction to the Fe-CO covalent bonding which increases as the number of the cyano groups increases, and the complexes become more negatively charged. This contribution decreases in going from Fe(0) to Fe(2+) complexes. Also, this contribution correlates very well with the C-O stretching frequencies. The Fe-CN bonds have much less pi-character (12-30%) than the Fe-CO bonds.
John T Tsalavoutis; Michael P Sigalas
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Publication Detail:
Type:  Journal Article    
Journal Detail:
Title:  Journal of computational chemistry     Volume:  31     ISSN:  1096-987X     ISO Abbreviation:  J Comput Chem     Publication Date:  2010 Jul 
Date Detail:
Created Date:  2010-05-31     Completed Date:  2010-09-09     Revised Date:  -    
Medline Journal Info:
Nlm Unique ID:  9878362     Medline TA:  J Comput Chem     Country:  United States    
Other Details:
Languages:  eng     Pagination:  1969-78     Citation Subset:  IM    
Copyright Information:
2010 Wiley Periodicals, Inc.
Laboratory of Applied Quantum Chemistry, Department of Chemistry, Aristotle University of Thessaloniki, 541 24 Thessaloniki, Greece.
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MeSH Terms
Cyanides / chemistry*
Iron Carbonyl Compounds / chemistry*
Iron Compounds / chemistry*
Models, Molecular
Quantum Theory
Reg. No./Substance:
0/Cyanides; 0/Iron Compounds; 0/Ligands; 13463-40-6/Iron Carbonyl Compounds

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