Compounds with Low‐Valent p‐Block Elements for Small Molecule Activation and Catalysis

Abstract

The past decade has witnessed staggering progress in the chemistry of compounds with low‐valent main‐group elements. Although these discoveries are mostly fundamental by nature, these compounds show promising reactivity towards small molecule activation. The reactivity of these compounds stems from the modest HOMO–LUMO energy gap; a characteristic known for the transition metals. The journey began in 2005 with the facile activation of dihydrogen by an alkyne analog of germanium [ArGe≡GeAr; Ar=2,6‐Trip2‐C6H3 (Trip=2,4,6‐iPr3‐C6H2)]. Subsequently, tremendous progress has been achieved in understanding and elucidating the potential of these compounds to activate small molecules as well as to use them in a variety of stoichiometric and catalytic transformations. In this review, we focus on developments in the activation of H2, NH3, CO, and CO2 by compounds with multiply bound or open shell main‐group elements. Emphasis will be given to their catalytic activity.

Cleavage of Two Hydrogen Molecules by Boryldisilenes

“…This is consistent with NBO and naturalr esonance theory (NRT) [14] analyses of 1' opt which has methyl and 2,6-diisopropylphenyl groups insteado fa damantyl andT ip groups. These two interactions are similar to the interactions of H 2 with other main-group species, such as frustrated Lewis pairs, [3a, 17] heavy alkynes, [1,2] carbenes, [3b] and transition metals. The weake lectron donation from the amino group to the Si= Si double bond is probably due to the large energy difference between the occupied2 p( lone pair) orbital of the amino group and the p(Si=Si)o rbital.…”

“…[1] The first example of cleavage of H 2 by using ac ompound consistingo famain group element was reported by Power et al and was the reactiono facompound with ag ermanium-germanium triple bond (digermyne) with H 2 (1 atm) at room temperature. [1] The first example of cleavage of H 2 by using ac ompound consistingo famain group element was reported by Power et al and was the reactiono facompound with ag ermanium-germanium triple bond (digermyne) with H 2 (1 atm) at room temperature.…”

S–H Bond Activation in Hydrogen Sulfide by NHC-Stabilized Silyliumylidene Ions

“…Low-valent main group chemistry is a rapidly developing field and the wealth of new structural motifs, which have been isolated in the past two decades, have increasingly gained interest in using these species for the activation of small molecules and, potentially, for catalysis (for representative reviews see [1][2][3][4][5][6][7]). Key to these developments have been the usage of suitable synthetic methodologies in combination with thermodynamic and kinetic stabilization by appropriately chosen ligands.…”

Synthesis, Structure and Chemistry of Mono‐ and Digallane Complexes Supported by N,O‐Ketimine Ligand

“…Compounds with low‐valent main group elements, especially the group 13 and 14 are of particular interest owing to their importance in activating a range of small molecules such as H 2 , CO, CO 2 , NH 3 , and H 2 O and associated catalytic processes . In 2009 Power et al .…”