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London dispersion forces in sterically crowded inorganic and organometallic molecules

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Abstract

London dispersion forces are the weakest component of Van der Waals interactions. They arise from attractions between instantaneously induced dipoles on neighbouring atoms. Their relative weakness, in particular for light atoms, such as hydrogen, has led to their importance being largely ignored in discussions of molecular stability and reactivity. This Review highlights the influence of these attractive forces — usually between C–H moieties in ancillary ligands — on the physical and chemical properties of organometallic and inorganic molecules. We feature recent examples of organic species that have informed current thinking and follow with a discussion of several prominent inorganic and organometallic complexes wherein dispersion forces have been explicitly identified or calculated. These forces strongly influence the behaviour of such complexes and often have a defining structural role. Attention is also drawn to several compounds in which significant attractive dispersion forces are probably present but have not been investigated.

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Figure 1: Examples of large, sterically crowded organic and inorganic substituents.
Figure 2: Timeline of the relevant advances in the study of London dispersion forces in organic and inorganic compounds.
Figure 3: London dispersion force effects in organic molecules.
Figure 4: London dispersion force effects in superilyl and related groups.
Figure 5: London dispersion force effects on molecules with multiple bonds between main group elements.
Figure 6: London dispersion force effects in transition and lanthanide metal complexes.

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Acknowledgements

The authors are grateful to the David Parkin Visiting Professorship at the University of Bath (P.P.P.), the English-Speaking Union Lindemann Trust Fellowship (D.J.L.), the US National Science Foundation (CHE-1565501) and M. Hill for his generosity, invaluable advice and support.

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Glossary

Terphenyls

In this Review, a terphenyl ligand consists of a central aryl ring substituted by two further aryl rings at the ortho (that is, flanking) positions relative to the carbon atom (ipso) through which the terphenyl ligand is attached to the reactive centre. They are denoted by the abbreviation Ar R n , where the superscript R refers to the type of substituents on the aryl rings and the numeral indicates the number of R substituents present: for example, Ar\(^{{\rm ME}_{\rm 6} } \) = C6H3-2,6-(C6H2-2,4,6-Me3)2 and Ar\(^{i{\rm -Pr}_{\rm 4} } \) = C6H3-2,6-(C6H3-2,6-iPr6)2.

Extended transition state–natural orbitals for chemical valence

(ETS–NOCV). A scheme for the analysis of chemical bonds based on the decomposition of the bonding on the basis of charge and energy90.

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Liptrot, D., Power, P. London dispersion forces in sterically crowded inorganic and organometallic molecules. Nat Rev Chem 1, 0004 (2017). https://doi.org/10.1038/s41570-016-0004

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