Interpretation of Tolman electronic parameters in the light of natural orbitals for chemical valence

Literature Information

Publication Date 2017-01-25
DOI 10.1039/C6CP07793E
Impact Factor 3.676
Authors

G. Attilio Ardizzoia, Stefano Brenna


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Abstract

Understanding the nature and the strength of metal–ligand interactions in d- and f-block metal complexes has always been a central issue for both synthetic and theoretical chemists. These interactions are usually described according to the well accepted Dewar–Chatt–Duncanson model, and thus over the years numerous research groups directed their efforts to shed light on the role of σ- and π-contributions. Among others, the electronic parameter introduced by Tolman in the 1970s represents a milestone in this field. Herein we present a quantitative description of the nickel–phosphine bond in Tolman's nickel(0) carbonyl complexes. The combination of Natural Orbitals for Chemical Valence with Energy Decomposition Analysis resulted in the definition of a new parameter (Tphos) which comprises all the energetic contributions needed to describe the nickel–phosphine bond and thus stands as a reliable descriptor of the electronic properties of phosphines. Moreover, steric effects of phosphines (i.e. Tolman's cone angles) have been considered too, and a linear relation including Ni–P bond distances, Tphos and cone angle has been found.

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Physical Chemistry Chemical Physics

Physical Chemistry Chemical Physics
CiteScore: 5.5
Self-citation Rate: 10.3%
Articles per Year: 3036

Physical Chemistry Chemical Physics (PCCP) is an international journal co-owned by 19 physical chemistry and physics societies from around the world. This journal publishes original, cutting-edge research in physical chemistry, chemical physics and biophysical chemistry. To be suitable for publication in PCCP, articles must include significant innovation and/or insight into physical chemistry; this is the most important criterion that reviewers and Editors will judge against when evaluating submissions. The journal has a broad scope and welcomes contributions spanning experiment, theory, computation and data science. Topical coverage includes spectroscopy, dynamics, kinetics, statistical mechanics, thermodynamics, electrochemistry, catalysis, surface science, quantum mechanics, quantum computing and machine learning. Interdisciplinary research areas such as polymers and soft matter, materials, nanoscience, energy, surfaces/interfaces, and biophysical chemistry are welcomed if they demonstrate significant innovation and/or insight into physical chemistry. Joined experimental/theoretical studies are particularly appreciated when complementary and based on up-to-date approaches.

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