Understanding Cooperativity in Homo‐ and Heterometallic Complexes: From Basic Concepts to Design

Abstract

Cooperative effects have attracted considerable attention in recent years. These effects are ubiquitous in chemistry and biology and can govern interactions of proteins with other biomolecules, mechanism of supramolecular recognition and polymerization, catalysis, assembly of compounds on surfaces, and physical properties such as magnetic, electronic or optical properties, e.g. Consequently, the understanding of cooperative effects can lead to a structure‐property relation that can pave the way to future applications in various research areas; however, with regard to cooperative effects in homo‐ and heterometallic complexes, we still are at the beginning of understanding. Nevertheless, concepts to describe cooperativity of metal centers as well as methodologies to investigate and model these effects have emerged over the last years. This concept article gives an overview of these existing concepts, approaches, and strategies to understand cooperative effects in homo‐ and heterometallic complexes. Special emphasis is put on concepts to define cooperative effects, their quantification, as well as methods to investigate cooperative effects.

P(v)-bis(amidophenolate) ligand cooperation: stoichiometric CO-bond cleavage in aldehydes and ketones

“…Among other advantages, these catalysts often serve as environmentally benign alternatives to previously developed systems in which a possible active role of the ligand was not considered. 1 However, and despite that undeniable impact, the exploitation of cooperativity in homogeneous catalysis has been mostly limited to transition metal-mediated processes; the transfer of such designing principles to p-block element-based catalysis is, in comparison, underdeveloped. 2 Remarkable exceptions are Radosevich catalytic hydrogenations and hydroborations using geometrically distorted phosphoramidites and phosphorus triamides, 3 the hydroboration of aldehydes and ketones mediated by N-heterocyclic germylenes, 4 and the digallane-catalysed hydroamination of alkynes introduced by Fedushkin, 5 among others.…”