Alkali Metal Metal(ates) Containing Divalent Earth Abundant Transition Metals

Abstract

Recent advances in cooperative chemistry have shown the enormous potential of main group heterobimetallic complexes for the functionalisation of aromatic molecules. Going beyond main group metal chemistry, here we provide an overview on the synthesis, structure and reactivity of bimetallic complexes which combine an alkali-metal (AM= Li, Na) with a divalent earth-abundant transition metal (M= Mn, Fe, Co, Ni), containing the utility silyl amide HMDS (HMDS = N(SiMe3)2). Advancing the understanding on how cooperative effects operate in these bimetallic (ate) systems, selected examples of their applications in deprotonative metalation are also discussed with special emphasis on the constitution of the metalated intermediates.

Cooperative activation of carbon–hydrogen bonds by heterobimetallic systems

“…Among the products formed are notably inverse-crown complexes, 133 which have been extensively reviewed elsewhere. 126,127 Hevia and coworkers have considerably extended the alkalimetal -ate chemistry [136][137][138] and very recently reported the dehydrometallation of fluoroarenes mediated by cobalt alkalimetal amides (Fig. 37).…”

“…Hevia and coworkers have considerably extended the alkali–metal - ate chemistry 136–138 and very recently reported the dehydrometallation of fluoroarenes mediated by cobalt alkali–metal amides (Fig. 37).…”

Interaction and Energy Decomposition Analyses to Predict Stability of Tetraaryl Square Planar Cobalt Complexes

“…1,3‐diflurorobenzene, 1,2,3‐triflurorobenzene, 1,3,5‐triflurorobenzene, 1,3,4,5‐tetraflurorobenzene and 1,2,3,4‐tetraflurorobenzene), when other non‐doubly F‐substituted arenes in ortho position are used, such as 1,2,3,4‐tetrafluorobenzene ( Ar FH ), 1,3,5‐trichlorobenzene ( Ar Cl ), and 1,4‐dibromo‐2,5‐difluorobenzene ( Ar Br ), metalation occurs to give the relevant [NaCo(HMDS) 2 (Ar)] intermediates. These species can be isolated and characterized, [13,17] but no ligand redistribution is observed, failing to furnish square planar complexes.…”

Silicon–nitrogen bond formation via dealkynative coupling of amines with bis(trimethylsilyl)acetylene mediated by KHMDS

“…[1][2][3][4] Indeed, these compounds wherein the silyl moiety is directly bonded to nitrogen have found broad application, including the utilization as bases, 5 silylating agents (e.g., needed for the protection of reactive groups such as OH), [6][7][8] and ligands for several complexes (Figure 1, a). [9][10][11][12][13][14][15] Aminosilanes can be readily accessed via welldeveloped stoichiometric methods. Here, Si-N bond is formed by aminolysis of chlorosilanes with amines (Figure 1, b).…”

“…1a). [9][10][11][12][13][14][15] Aminosilanes can be readily accessed via welldeveloped stoichiometric methods. Here, the Si-N bond is formed by aminolysis of chlorosilanes with amines (Fig.…”