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

Ferrocene Orientation Determined Intramolecular Interactions Using Energy Decomposition Analysis

1
Molecular Model Discovery Laboratory, Department of Chemistry and Biotechnology, Faculty of Science, Engineering and Technology, Swinburne University of Technology, Hawthorn, Melbourne 3122, Australia
2
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)
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Abstract

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
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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).

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

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