Cooperative Bond Activation and Catalytic Reduction of Carbon Dioxide at a Group 13 Metal Center

Abstract

A single-component ambiphilic system capable of the cooperative activation of protic, hydridic and apolar HX bonds across a Group 13 metal/activated β-diketiminato (Nacnac) ligand framework is reported. The hydride complex derived from the activation of H2 is shown to be a competent catalyst for the highly selective reduction of CO2 to a methanol derivative. To our knowledge, this process represents the first example of a reduction process of this type catalyzed by a molecular gallium complex.

Boron-mediated activation of carbon dioxide

“…The ruthenium complex 47 is notably isolated from the reaction of a related hydride complex with CO 2 . Hill et al [48] and Aldridge et al [58] reported the same transformation using complexes 48-50, which are the first non-transition metal based catalysts of this reaction, although less efficient. [61].…”

On the non-innocence of “Nacnacs”: ligand-based reactivity in β-diketiminate supported coordination compounds

“…230,231 Since subsequent negative charge is lying on the CH 2 unit, in some instances the ligand rearranges intramolecularly to bind in a N,C-chelating mode (Scheme 57). Deprotonation of the β-Me position 9.1 A diverse array of structures BDI ligands featuring β-Me groups are well known to undergo deprotonation at the β-Me carbon position.…”

“…246 In these reactions, the exocyclic methylene group behaves as a nucleophile and plays the role of the proton or silyl-group acceptor. 231 Interestingly the germylene compound (#BDI*)Ge reacts with 1,2-dibromoethane or Br 2 to yield the C-C homocoupled dimer of two germylene units, shown on Scheme 71top. 133 Aldridge and co-workers have recently extended this chemistry to group 13 systems, which possesses the ability to heterolytically cleave acidic and hydridic H-X (X = NH 2 , SH, SiH 3 ) polar bonds, but also add non-polar molecules such as H 2 across the metal-(#BDI) framework.…”

Anorganische Molekülchemie

“…23) Indium(III)-Halogenide katalysieren inzwischen häufiger organische Reaktionen. Insbesondere Kationen des Typs [InX 2 ] + zeigen bei einigen Transformationen wie Polycyclisierungen erhöhte Aktivitäten.…”