A Stable Calcium Alumanyl

Abstract

A seven‐membered N,N′‐heterocyclic potassium alumanyl nucleophile is introduced and utilised in the metathetical synthesis of Mg−Al and Ca−Al bonded derivatives. Both species have been characterised by experimental and theoretical means, allowing a rationalisation of the greater reactivity of the heavier group 2 species implied by an initial assay of their reactivity.

Contrasting the Mechanism of H2Activation by Monomeric and Potassium‐Stabilized Dimeric AlIComplexes: Do Potassium Atoms Exert any Cooperative Effect?

“…On the other hand, although the nucleophilic nature of the complex involving these species cannot be ignored as being highly reactive toward electrophiles (such as MeOTf or MeI), the computed electron population for the aluminum centers exhibit the presence of positively charged centers, + 0.70 e j j (in M) and + 0.75 e j j (both Al atoms in D), in agreement with similar aluminyl complexes. [67] Even the Al atoms show relatively similar charges as the K + atoms in the dimeric structure + 0.80 e j j, and therefore pure stabilizing electrostatic interactions between the aluminum and potassium centers are dismissed. However, dispersion and potential lonepair(Al)⋯K + interactions are still present.…”

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

“… 34 However, the experimentally synthesized and characterized aluminyl nucleophiles depicted in Scheme 1 sufficiently differ each other from a structural point of view to our aim. Anion I is a three-coordinated Al species, anions II and III are two-coordinated Al species supported by bidentate six- and seven-membered diamino ligands, K 2 [Al( Si NON)] 2 ( Si NON = {O(SiMe 2 NDipp) 2 }) 3 and K 2 [Al(NCCN)] 2 (NCCN = {CH 2 SiMe 2 N(Dipp)} 2 , Dipp = 2,6-iPr 2 C 6 H 3 ), 4 respectively. Anion IV is a two-coordinated Al by the chelating β-diketiminate six-membered planar ligand, where a backbone Me group is deprotonated K[Al( Dipp BDI-H)] ( Dipp BDI-H = H 2 C C(N-Dipp)-C(H) C(Me)-N-Dipp).…”

“…1,2 Shortly aer this discovery, the family of aluminyl anions enlarged to include ve additional members (species II, III, IV, V and VI in Scheme 1). [3][4][5][6][7] Synthesis, structures and reactivity for this series of six aluminyl anions and their associated metal complexes were reviewed and reactions including nucleophilic substitution, oxidative addition, cycloaddition, reductions and oxidations were summarized, with special focus on the C-H and C-F activation, small molecules activation and the ring opening of aromatics. 8 Metal-aluminyl complexes are of particular interest, since the electronic properties of aluminyls closely resemble those of carbenes, which represent a class of ubiquitous and extremely versatile ligands in coordination chemistry.…”

“…1,2 Shortly after this discovery, the family of aluminyl anions enlarged to include five additional members (species II , III , IV , V and VI in Scheme 1). 3–7 Synthesis, structures and reactivity for this series of six aluminyl anions and their associated metal complexes were reviewed and reactions including nucleophilic substitution, oxidative addition, cycloaddition, reductions and oxidations were summarized, with special focus on the C–H and C–F activation, small molecules activation and the ring opening of aromatics. 8…”

Substituent Effects on Aluminyl Anions and Derived Systems: A High-Level Theory

“…Catalyst IV was found to activate H 2 in benzene solution at ambient conditions or 2 atm of this gas in the solid state. Moreover, the activation of C–H bonds in benzene and formation of Al–Al and Al–Mg bonds were also observed. , Following this report, several stabilized aluminyl anions have been prepared to be subject to experimental and theoretical characterizations. − …”