Next Article in Journal
Effect of Oxide Coating on Performance of Copper-Zinc Oxide-Based Catalyst for Methanol Synthesis via Hydrogenation of Carbon Dioxide
Previous Article in Journal
A Novel Biodegradable Polycaprolactone Fixator for Osteosynthesis Surgery of Rib Fracture: In Vitro and in Vivo Study
Previous Article in Special Issue
1-(Triethoxysilyl)buta-1,3-dienes—New Building Blocks for Stereoselective Synthesis of Unsymmetrical (E,E)-1,4-Disubstituted 1,3-dienes
Article Menu

Export Article

Open AccessArticle
Materials 2015, 8(11), 7723-7737; doi:10.3390/ma8115419

Ferrocene Orientation Determined Intramolecular Interactions Using Energy Decomposition Analysis

Molecular Model Discovery Laboratory, Department of Chemistry and Biotechnology, Faculty of Science, Engineering and Technology, Swinburne University of Technology, Hawthorn, Melbourne 3122, Australia
National Computational Infrastructure, Australian National University, Canberra 0200, Australia
Author to whom correspondence should be addressed.
Academic Editor: Łukasz John
Received: 16 October 2015 / Revised: 9 November 2015 / Accepted: 9 November 2015 / Published: 16 November 2015
(This article belongs to the Special Issue Organometallic Compounds 2015)
View Full-Text   |   Download PDF [244 KB, uploaded 16 November 2015]   |  


Two very different quantum mechanically based energy decomposition analyses (EDA) schemes are employed to study the dominant energy differences between the eclipsed and staggered ferrocene conformers. One is the extended transition state (ETS) based on the Amsterdam Density Functional (ADF) package and the other is natural EDA (NEDA) based in the General Atomic and Molecular Electronic Structure System (GAMESS) package. It reveals that in addition to the model (theory and basis set), the fragmentation channels more significantly affect the interaction energy terms (ΔE) between the conformers. It is discovered that such an interaction energy can be absorbed into the pre-partitioned fragment channels so that to affect the interaction energies in a particular conformer of Fc. To avoid this, the present study employs a complete fragment channel—the fragments of ferrocene are individual neutral atoms. It therefore discovers that the major difference between the ferrocene conformers is due to the quantum mechanical Pauli repulsive energy and orbital attractive energy, leading to the eclipsed ferrocene the energy preferred structure. The NEDA scheme further indicates that the sum of attractive (negative) polarization (POL) and charge transfer (CL) energies prefers the eclipsed ferrocene. The repulsive (positive) deformation (DEF) energy, which is dominated by the cyclopentadienyle (Cp) rings, prefers the staggered ferrocene. Again, the cancellation results in a small energy residue in favour of the eclipsed ferrocene, in agreement with the ETS scheme. Further Natural Bond Orbital (NBO) analysis indicates that all NBO energies, total Lewis (no Fe) and lone pair (LP) deletion all prefer the eclipsed Fc conformer. The most significant energy preferring the eclipsed ferrocene without cancellation is the interactions between the donor lone pairs (LP) of the Fe atom and the acceptor antibond (BD*) NBOs of all C–C and C–H bonds in the ligand, LP(Fe)-BD*(C–C & C–H), which strongly stabilizes the eclipsed (D5h) conformation by −457.6 kcal·mol−1. View Full-Text
Keywords: ferrocene; eclipsed and staggered conformers; energy decomposition analysis; natural bond orbital scheme; intramolecular interaction; quantum mechanical models ferrocene; eclipsed and staggered conformers; energy decomposition analysis; natural bond orbital scheme; intramolecular interaction; quantum mechanical models

This is an open access article distributed under the Creative Commons Attribution License which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited. (CC BY 4.0).

Scifeed alert for new publications

Never miss any articles matching your research from any publisher
  • Get alerts for new papers matching your research
  • Find out the new papers from selected authors
  • Updated daily for 49'000+ journals and 6000+ publishers
  • Define your Scifeed now

SciFeed Share & Cite This Article

MDPI and ACS Style

Wang, F.; Islam, S.; Vasilyev, V. Ferrocene Orientation Determined Intramolecular Interactions Using Energy Decomposition Analysis. Materials 2015, 8, 7723-7737.

Show more citation formats Show less citations formats

Related Articles

Article Metrics

Article Access Statistics



[Return to top]
Materials EISSN 1996-1944 Published by MDPI AG, Basel, Switzerland RSS E-Mail Table of Contents Alert
Back to Top