Carbonite chemistry series#

The same reaction at higher concentrations additionally led to the formation of a unique hexanuclear NiII complex containing both oxalate and mesoxalate (4‐) ligands. If the number of K equivalents used in the reaction with is decreased from three to half an equivalent, the deprotonated part of the precursor enters into a complex reaction sequence with formation of K and. Furthermore, in case of K⁺, the + shell around the Ni‐CO22‐ entity was shown to have a large impact on its stabilization and behavior.

Carbonite chemistry series#

The results point to a decrease of CO2 activation within the series Li, Na, and K, which is also reflected in the reactivity with Me3SiOTf leading to the liberation of CO and formation of a Ni−OSiMe3 complex. The complexes M32 (M=Li, Na, K), synthesized by deprotonation of a nickel formate complex with the corresponding amides M, feature a NiII−CO2²⁻ core surrounded by Lewis‐acidic cations (M⁺) and the influence of the latter on the behavior and reactivity was studied. Mesoxalate formation from individual CO2 units is so far unprecedented. As in Part 1, for each tin compound reported and when described in the original study, the structural descriptions are supplemented by synthetic conditions and spectroscopic data.Ī deceptively simple proton abstraction from nickel‐bound formate not only prepares the resulting CO2²⁻ unit for the release of CO in contact with electrophiles but opens up unique complex reaction schemes including reduction of nickel(II) to nickel(I) and coupling of CO2 units to give oxalate and mesoxalate. The last chapter is devoted to X-ray structures of transition metal/tin CO2 complexes exhibiting metallocarboxylato ligands. In the frame of a second part, the present review carries on to explore CO2 derivatives of molecular tin compounds by describing successively the complexes with carbamato, formato, and phosphinoformato ligands, and obtained from insertion reactions of carbon dioxide into Sn–X bonds (X = N, H, P, respectively). Interestingly, this first collection revealed that most of the compounds listed were isolated in the context of studies devoted to the reactivity of tin precursors towards carbon dioxide, at atmospheric pressure or under pressure, thus highlighting the suitable disposition of Sn to fix CO2. Part 1: Hemicarbonato and Carbonato Complexes”, Inorganics2020, 8, 31-based on crystallographic data available from the Cambridge Structural Database. Single-crystal X-ray diffraction structures of organotin compounds bearing hemicarbonate and carbonate ligands were recently reviewed by us-“CO2 Derivatives of Molecular Tin Compounds.