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Bonding Situation of σ‐E−H Complexes in Transition Metal and Main Group Compounds
Author(s) -
Ríos Pablo,
Conejero Salvador,
Fernández Israel
Publication year - 2022
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.202201920
Subject(s) - atoms in molecules , chemistry , transition metal , natural bond orbital , density functional theory , molecule , group (periodic table) , quantum chemical , computational chemistry , crystallography , organic chemistry , catalysis
Abstract The ambiguous bonding situation of σ‐E−H (E=Si, B) complexes in transition metal compounds has been rationalized by means of Density Functional Theory calculations. To this end, the combination of the Energy Decomposition Analysis (EDA) method and its Natural Orbital for Chemical Valance (NOCV) extension has been applied to representative complexes described in the literature where the possible η 1 versus η 2 coordination mode is not unambiguously defined. Our quantitative analyses, which complement previous data based on the application of the Quantum Theory of Atoms in Molecules (QTAIM) approach, indicate that there exists a continuum between genuine η 1 and η 2 modes depending mainly on the strength of the backdonation. Finally, we also applied this EDA‐NOCV approach to related main‐group species where the backdonation is minimal.