Structures and Bonding Situation of Iron Complexes of Group‐13 Half‐Sandwich ECp* (E = B to Tl) Based on DFT Calculations

Abstract

Quantum chemical calculations at the BP86 level with various basis sets (SVP, TZVPP, and TZ2P+) were carried out for the Fe(CO) 4 of group-13 half-sandwich ECp* [Fe(CO) 4 -ECp*] (Fe4-E) (E = B to Tl). The chemical bonding of the Fe(CO) 4 -ECp* bond was analyzed with charge-and energy decomposition methods. The calculated equilibrium structures of complexes Fe4-E show that the ligands ECp* are bonded in an end-on way to the fragment Fe(CO) 4 in Fe4-E with E = B to Ga. The compound Fe4-In has a distorted end-on ligand InCp*. In contrast, Fe4-Tl has a side-on bonded ligand TlCp*.

Structure and property of complexes of group 13 diyl containing subvalent silylone using energy decomposition analysis with natural orbitals for chemical valence

“…This remains true for each of the five X-C bonds to the carbon atoms of the Cp* rings, which exhibits between 2.235 and 2.286 Å for W5-SiAl, 2.305 and 2.372 Å for W5-SiGa, 2.485 and 2.537 Å for W5-SiIn, and then 2.643 and 2.885 Å for W5-SiTl. The calculated equilibrium structures of complexes W5-SiX show that the ligands SiX are bonded in a tilted orientation relative to the fragment W(CO) 5 which the bending angle, , is 141.3 in boron complexes W5-SiB and becomes much more acute in the heavier system for W5-SiIn ( = 107.9), and slightly increases for W5-SiTl adduct ( = 117.8).…”

“…The schemes of combined energy decomposition analysis (EDA) [22] and charge of natural orbitals for chemical valence (NOCV) [10,11] were used to consider the bonding of the complexes investigated. The EDA decomposes the instantaneous interaction energy, ΔE int , of the bond W(CO) 5 -Si(XCp*) 2 from the two moieties [W(CO) 5 ] and [Si(XCp*) 2 ] as interacting fragments into three main components:…”

“…The W(CO) 5 -Si(XCp*) 2 complexes were optimized using the Amsterdam Density Fuctional (ADF) program package 2016.01. [23] The Becke-Perdew exchange-correlation functional (BP86) in conjunction was applied with a triple-zeta-quality basis set using uncontracted Slater-type orbitals (STOs) augmented by two sets of polarization function, with a frozen-core approximation for the core electrons.…”

“…[25] Scalar relativistic effects were incorporated by applying the zeroth-order regular approximation (ZORA). [26] The chemical bond via energy terms and charge transfers of the W-Si bonds in W(CO) 5 -Si(XCp*) 2 complexes using EDA-NOCV under C 1 symmetric geometries were examined at the BP86 [27] /TZ2P+ level of theory.…”

“…[1][2][3] It has been known that the classification of ligands according to their donor-acceptor properties permits for understanding the detailed electronic structure and bonding for presaging and rationalizing reactivity of complexes. [3][4][5] The many useful and available schemes were applied in the chemical bonding which emphasizes clearly different from the aspects of bonding, inclusive of Natural Bond Orbitals (NBO), [6] Atoms in Molecules (AIM), [7] Charge Decomposition Analysis (CDA). [8] However, separation of the donation-back donation or donoracceptor effects is often a challenge for experimental basis because donor-acceptor properties are usually drawn indirectly.…”