On the reactivity of Al-group 11 (Cu, Ag, Au) bonds

Abstract

.Reactions of the seven-membered heterocyclic potassium diamidoalumanyl, [K{Al(SiNDipp)}]2 (SiNDipp = {CH2SiMe2NDipp}2; Dipp = 2,6-di-isopropylphenyl), with a variety of Cu(I), Ag(I) and Au(I) chloride N-heterocyclic carbene (NHC) adducts are described. The...

Unraveling differences in aluminyl and carbene coordination chemistry: bonding in gold complexes and reactivity with carbon dioxide

“…In addition, despite some differences that can be explained in terms of steric hindrance of the aluminyl ligand, the two reaction steps (namely, the Au–Al nucleophilic attack to CO 2 and CO 2 attack to electrophilic Al) feature activation barriers of comparable amount and similarly stabilized intermediates/products, highlighting that this reactivity is poorly controlled by electronic effects associated with the different geometrical arrangement of the aluminyl scaffold, which is in line with recent experimental evidence. 65 …”

Reactivity of Unsupported Transition Metal-Aluminyl Complexes: A Nucleophilic TM-Al Bond

“…). − Indeed, the TM-aluminyl complexes have shown their potential in small-molecule activation in recent studies, as exemplified by their insertion reactions with heteroallenes like carbon dioxide (CO 2 ) ( vide infra ). Because of the possible implication of TM-aluminyl complexes in catalysis, they have recently attracted increasing attention in the aspects of synthesis, reactivity, and electronic structure studies. − …”

“…Among those TM-aluminyl complexes reported to react with heteroallenes, there are simple structures with a clear TM–Al σ bond ,,− and more sophisticated structures with extensive bridging across the TM center and the aluminyl unit. − The focus of this study will be on the understanding of reactivity for those simpler cases with an unsupported TM–Al bond, in which there should be less influence from the other coordinations and it would allow us to pinpoint the source of reactivity.…”

Isolating elusive ‘Al(μ-O)M’ intermediates in CO2reduction by bimetallic Al–M complexes (M = Zn, Mg)

“…1). The aluminium fragments have been partnered with Zn, 9 and the coinage metals (Cu, Ag, Au) 10 to afford complexes containing unsupported Al– M bonds ( I ). Reaction of I with CO 2 proceeds with insertion into the Al– M bond to afford the corresponding dioxocarbene ( II ), the mechanism of which has been studied computationally.…”