Understanding the chemical bonding in sandwich complexes of transition metals coordinated to nine-membered rings: energy decomposition analysis and the donor–acceptor charge transfers

2021 ◽  
Vol 140 (9) ◽  
Author(s):  
Moncef Khireche ◽  
Bachir Zouchoune ◽  
Azedine Ferhati ◽  
Hacene Nemdili ◽  
Mohamed Amine Zerizer
Keyword(s):  
Transition Metals ◽  
Chemical Bonding ◽  
Decomposition Analysis ◽  
Energy Decomposition Analysis ◽  
Energy Decomposition ◽  
Sandwich Complexes ◽  
Complexes Of Transition Metals ◽  
Donor Acceptor

scholarly journals Variational Energy Decomposition Analysis of Chemical Bonding. 1. Spin-Pure Analysis of Single Bonds

2016 ◽  
Vol 12 (10) ◽  
pp. 4812-4820 ◽  
Author(s):  
Daniel S. Levine ◽  
Paul R. Horn ◽  
Yuezhi Mao ◽  
Martin Head-Gordon
Keyword(s):  
Chemical Bonding ◽  
Decomposition Analysis ◽  
Energy Decomposition Analysis ◽  
Energy Decomposition ◽  
Single Bonds

Chemical bonding and aromaticity in metalloporphyrins,

2009 ◽  
Vol 87 (7) ◽  
pp. 1063-1073 ◽  
Author(s):  
Ferran Feixas ◽  
Miquel Solà ◽  
Marcel Swart
Keyword(s):  
Transition Metals ◽  
Chemical Bonding ◽  
Electrostatic Interactions ◽  
Density Functional ◽  
Decomposition Analysis ◽  
Outer Ring ◽  
Energy Decomposition Analysis ◽  
Central Metal ◽  
Ligand Interactions ◽  
Almost All

We report here the chemical bonding and aromaticity patterns in metalloporphyrins, which were obtained with density functional theory (DFT) calculations at the OPBE/TZP level. This level of theory was previously shown to be very accurate for determining spin-state splittings [J. Chem. Theory Comput. 2008, 4, 2057] of transition-metal complexes. We considered metalloporphyrins along the first-row transition metals (Sc–Zn) extended with alkaline-earth metals (Mg, Ca) and several second-row transition metals (Ru, Pd, Ag, Cd). An energy decomposition analysis was performed to study the metal–ligand interactions, which showed that almost all complexes are significantly stabilized through (covalent) orbital interactions. The only exception is with calcium as the central metal, which interacts with the porphyrin mainly through electrostatic interactions. Furthermore, we studied aromaticity patterns for these complexes by looking at a number of (structural and electronic) aromaticity descriptors, for both the inner-ring and outer-ring of the porphyrin and of the pyrroles. The inner-ring (N16) aromaticity is shown to be unaffected by metal complexation, while the outer-ring (N20) and the pyrrole (N5) aromaticities are found to increase significantly in the metal coordinated porphyrins.

Bonding Situation in Dimeric Group 15 Complexes [(NHC)2(E2)] (E = N–Bi)

2014 ◽  
Vol 69 (7) ◽  
pp. 385-395 ◽  
Author(s):  
Nicole Holzmann ◽  
Gernot Frenking
Keyword(s):  
Density Functional ◽  
Decomposition Analysis ◽  
Borderline Case ◽  
Basis Sets ◽  
Energy Decomposition Analysis ◽  
Chemical Bonds ◽  
Energy Decomposition ◽  
Functional Theory ◽  
Donor Acceptor ◽  
Dinitrogen Complex

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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