Element‐Ligand Cooperativity with p‐Block Elements

Metal‐ligand cooperativity (MLC) had a tremendous impact on d‐block metal‐mediated bond activation and homogeneous catalysis. Is this concept translatable to the elements of the p‐block? Are there analogies already at hand? In this review, we describe contributions in which a p‐block element (group...

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Bibliographic Details
Published in:European journal of inorganic chemistry Vol. 2020; no. 32; pp. 3030 - 3047
Main Authors: Greb, Lutz, Ebner, Fabian, Ginzburg, Yael, Sigmund, Lukas M.
Format: Journal Article
Language:English
Published: Weinheim Wiley Subscription Services, Inc 31.08.2020
Subjects:
Activation
Analogies
Bond activation
Catalysis
Frustrated Lewis pairs
Homogeneous catalysis
Inorganic chemistry
Ligands
Metal‐ligand cooperativity
Molecular orbitals
P‐Block elements
Substrates
Transition metals
ISSN:1434-1948, 1099-0682
Online Access:Get full text
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Summary:Metal‐ligand cooperativity (MLC) had a tremendous impact on d‐block metal‐mediated bond activation and homogeneous catalysis. Is this concept translatable to the elements of the p‐block? Are there analogies already at hand? In this review, we describe contributions in which a p‐block element (group 13–15) and its ligand (surrounding molecular framework) operate synergistically in a substrate activation or a catalytic cycle. This activity is termed element‐ligand cooperativity (ELC), in correspondence to MLC. After the concepts of p‐block low‐valent states and frustrated Lewis pairs mimicking the ambiphilic reactivity of transition metals, the spatial proximity of nucleophilic and electrophilic reaction sites and a small HOMO‐LUMO gap in a p‐block ELC complex might offer yet another approach. Selected examples shall illustrate common reactivities of ELC, disclose conceptual analogies with d‐block MLC, and outline shortcomings in this field. Element‐ligand cooperativity (ELC) is an increasingly utilized tool in p‐block element chemistry for bond activation reactions and catalysis. This review compiles manifold examples of ELC for elements of groups 13 to 15, addresses the vague borderline between ELC and intramolecular FLP chemistry, and highlights analogies to the parent field of transition metal‐ligand cooperativity.
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ISSN:1434-1948
1099-0682
DOI:10.1002/ejic.202000449