Bonding Situation in Dimeric Group 15 Complexes [(NHC)2(E2)] (E = N–Bi)
-
Nicole Holzmann
and
Gernot Frenking
Quantum chemical calculations using density functional theory at the BP86 level in conjunction with triple-zeta polarized basis sets have been carried out for the title compounds. The nature of the bonding between the diatomic fragment and the NHC ligands is investigated with an energy decomposition analysis. The chemical bonds in the [(NHCMe)2(E2)] complexes can be discussed in terms of donor-acceptor interactions which consist of two NHCMe→E2←NHCMe donor components and two weaker components of the NHCMe←E2→NHCMe π backdonation. The out-of-phase (+)=(-) contribution of the s donation is always stronger than the in-phase (+)=(+) contribution. The electronic reference state of N2 in the dinitrogen complex [(NHCMe)2(N2)] is the highly excited 11Γg state which explains the anti-periplanar arrangement of the ligands. The gauche arrangement of the ligands in the heavier homologues [(NHCMe)2(E2)] (E = P-Bi) may be discussed using either the excited 11Γg state or the X1Σg+ ground state of E2 as reference states for the donor-acceptor bonds. The EDA-NOCV calculations suggest that the latter bonding model is better suited for the complexes where E = As-Bi while the phosphorus complex is a borderline case.
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- Theoretical Analysis of the Unusual Vicinal Effects on Electronic Circular Dichroism Spectra of Cobalt(III) Complexes with ED3A-Type and Related Ligands
- Bonding Situation in Dimeric Group 15 Complexes [(NHC)2(E2)] (E = N–Bi)
Articles in the same Issue
- Dedicated Editorial Communication: Jörg Fleischhauer 75
- Towards Correlated Sampling for the Fixed-Node Diffusion Quantum Monte Carlo Method
- Maxwell’s Demon Observing Creation of a Molecular Vibration
- Electronic and Magnetic Properties of the Graphene/Eu/Ni(111) Hybrid System
- The Conformation of Pentanoates in the Solid and in the Gas Phase
- The Role of Heme Chirality in the Circular Dichroism of Heme Proteins
- Convenient Small-Scale Preparation of p-Carborane by Pyrolysis of o-Carborane
- Computational Study of the Structure, the Flexibility, and the Electronic Circular Dichroism of Staurosporine – a Powerful Protein Kinase Inhibitor
- Quantum-Chemical Investigations on the Structural Variability of Anion–π Interactions
- Quantum-Chemical Ab Initio Calculations on Ala-(C5H5Al) and Galabenzene (C5H5Ga)
- A Short Review on the Magnetic Effects Occurring at Organic Ferromagnetic Interfaces Formed between Benzene-Like Molecules and Graphene with Ferromagnetic Surfaces
- Theoretical Analysis of the Unusual Vicinal Effects on Electronic Circular Dichroism Spectra of Cobalt(III) Complexes with ED3A-Type and Related Ligands
- Bonding Situation in Dimeric Group 15 Complexes [(NHC)2(E2)] (E = N–Bi)
