Interpretation of Tolman electronic parameters in the light of natural orbitals for chemical valence
Literature Information
G. Attilio Ardizzoia, Stefano Brenna
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.
Recommended Journals

Electroanalysis

Colloid Journal

Journal of the Indian Institute of Science

Critical Reviews in Solid State and Materials Sciences

Herald of the Russian Academy of Sciences

Polycyclic Aromatic Compounds

Heteroatom Chemistry

Journal of Chemical Sciences

Journal of Asian Natural Products Research

Biocatalysis and Biotransformation
Related Literature
Biocatalytic deuterium- and hydrogen-transfer using over-expressed ADH-‘A’: enhanced stereoselectivity and 2H-labeled chiral alcohols
Christian C. Gruber, Tina M. Poessl, Frank Niehaus, Juergen Eck, Reinhold Oehrlein, Andreas Hafner
DOI: 10.1039/B602487D
Scanning electrochemical microscopy under illumination: an elegant tool to directly determine the mobility of charge carriers within dye-sensitized nanostructured semiconductors
Biljana Bozic, Egbert Figgemeier
DOI: 10.1039/B601587E
Enantioselective conjugate addition of phenylboronic acid to enones catalysed by a chiral tropos/atropos rhodium complex at the coalescence temperature
Chiara Monti, Cesare Gennari, Umberto Piarulli
DOI: 10.1039/B508832A
Formation of layered titania and zirconia catalysed by surface-bound silicatein
Muhammad Nawaz Tahir, Patrick Théato, Werner E. G. Müller, Heinz C. Schröder, Alexandra Borejko, Simon Faiß, Andreas Janshoff, Joachim Huth, Wolfgang Tremel
DOI: 10.1039/B510113A
A platinum-catalyzed annulation reaction leading to medium-sized rings
Dirk Hildebrandt, Wiebke Hüggenberg, Matthias Kanthak, Tobias Plöger, Iris M. Müller, Gerald Dyker
DOI: 10.1039/B602498J
Anion-templated assembly of interpenetrated and interlocked structures
Paul D. Beer, Mark R. Sambrook, David Curiel
DOI: 10.1039/B516435B
Effect of tetrabutylphosphonium cation on the physico-chemical properties of amino-acid ionic liquids
Junko Kagimoto, Kenta Fukumoto, Hiroyuki Ohno
DOI: 10.1039/B600771F
Non-stoichiometry induced by differential oxygen/lone pair occupation in chiral bicyclic 1,1′-binaphthoxy cyclodiphosphazanes
Manab Chakravarty, Praveen Kommana, K. C. Kumara Swamy
DOI: 10.1039/B509327A
Metal complexes of selenophosphinates from reactions with (R2PSe)2Se: [M(R2PSe2)n] (M = ZnII, CdII, PbII, InIII, GaIII, CuI, BiIII, NiII; R = iPr, Ph) and [MoV2O2Se2(Se2PiPr2)2]
Chinh Q. Nguyen, Adekunle Adeogun, Mohammad Afzaal, Mohammad A. Malik, Paul O'Brien
DOI: 10.1039/B603198F
Sieving behaviour of nanoscopic pores by hydrated ions
Joohan Lee, Juhyoun Kwak
DOI: 10.1039/B601613H
You might also like
What are the main uses of 1H-Indazole-6-carbonitrile (CAS: 141290-59-7)?
1H-Indazole-6-carbonitrile finds applications in pharmaceuticals, where it serve...
How should waste containing Dioctyl (2E)-2-butenedioate (CAS: 2997-85-5) be handled?
Waste containing Dioctyl (2E)-2-butenedioate (CAS: 2997-85-5) should be collecte...
What industries use Sodium [(1,2-benzoxazol-3-ylmethyl)sulfonyl]azanide (CAS: 68291-98-5)?
Sodium [(1,2-benzoxazol-3-ylmethyl)sulfonyl]azanide is primarily used in pharmac...
Are there alternatives to Dimethyl 4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-2,6-pyridinedicarboxylate (CAS: 741709-66-0) in synthesis?
Dimethyl 4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-2,6-pyridinedicarboxyla...
How should waste containing 2-Fluoro-6-hydrazinopyridine (CAS: 80714-39-2) be handled?
Waste containing 2-Fluoro-6-hydrazinopyridine (CAS: 80714-39-2) should be manage...
What is 6-Formyl-2-pyridinecarboxylic acid (CAS: 499214-11-8)?
6-Formyl-2-pyridinecarboxylic acid is an organic compound with the molecular for...
What is the market or research trend for 3-(3,4-dimethoxyphenyl)-2,5-dimethyl-N-(2-morpholin-4-ylethyl)pyrazolo[1,5-a]pyrimidin-7-amine (CAS: 900874-91-1)?
Research trends for this compound indicate a focus on its potential applications...
How is 9H-Tribenzo[b,d,f]azepine (CAS: 29875-73-8) typically synthesized?
9H-Tribenzo[b,d,f]azepine is typically synthesized via a multi-step process invo...
How is 1-Cyclopropyl-7-ethoxy-6-fluoro-8-methoxy-4-oxo-1,4-dihydro-3-quinolinecarboxylic acid (CAS: 1797982-51-4) typically synthesized?
1-Cyclopropyl-7-ethoxy-6-fluoro-8-methoxy-4-oxo-1,4-dihydro-3-quinolinecarboxyli...
How should waste containing Methyl 3-oxo-1,2,3,4-tetrahydro-6-quinoxalinecarboxylate (CAS: 671820-52-3) be handled?
Waste containing Methyl 3-oxo-1,2,3,4-tetrahydro-6-quinoxalinecarboxylate (CAS: ...
Source Journal
Physical Chemistry Chemical Physics

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.

![Sodium 3-[(E)-(4-anilinophenyl)diazenyl]benzenesulfonate structure Sodium 3-[(E)-(4-anilinophenyl)diazenyl]benzenesulfonate structure](https://static.chemtradehub.com/structs/587/587-98-4-035f.webp)


