Unexpected formal insertion of CO₂ into the C–Si bonds of a zinc compound

Abstract

Reaction of [κ2-PR2C(SiMe3)Py]2Zn (R = Ph, 2a; iPr, 2b) with CO2 affords the products of formal insertion at the C–Si bond, [κ2-PR2CC(O)O(SiMe3)Py]2Zn (R = Ph, 3a; iPr, 3b). Insertion product 3b was structurally characterized. The reaction appears to be a stepwise insertion and rearrangement of CO2 based on kinetic data.

RuBisCO‐Inspired CO2 Activation and Transformation by an Iridium(I) Complex

“…Nevertheless,C O 2 fixation by RuBisCO involves some interesting features that could be adapted to facilitate CO 2 transformation by other metal complexes as well. [7] While magnesium is the metal of choice in this essential enzyme,this selection seems markedly influenced by the abundance of the Mg 2+ ion. Surprisingly, attempts to design RuBisCO-inspired model compounds with Mg 2+[5] and other metal ions [6] have focused on the carbamate formation step,although the CÀCbond formation between the second CO 2 and the substrate RuBP in its endiolate form is the key function of the enzyme.This makes enolates or related substance classes such as enamides promising substrates in small-molecule systems that aim for CÀCb ond formation rather than carbamylation.…”

“…Surprisingly, attempts to design RuBisCO-inspired model compounds with Mg 2+[5] and other metal ions [6] have focused on the carbamate formation step,although the CÀCbond formation between the second CO 2 and the substrate RuBP in its endiolate form is the key function of the enzyme.This makes enolates or related substance classes such as enamides promising substrates in small-molecule systems that aim for CÀCb ond formation rather than carbamylation. [7] While magnesium is the metal of choice in this essential enzyme,this selection seems markedly influenced by the abundance of the Mg 2+ ion. However,w hen targeting synthetic metal complexes that are able to incorporate two CO 2 molecules in analogy to the natural ideal, but without the help of aprotein shell as highly sophisticated multifunctional ligand, other metal ions appear to be better suited.…”

2‐Arylsilacyclobutane as a Latent Carbanion Reacting with CO2

“…Thecarbon atom within carbon dioxide is far less electrophilic than that contained within an aldehyde.A ddition of organosilicon compounds to carbon dioxide at the C À Si bond is limited to strongly nucleophilic derivatives such as al ithiated (phosphacyclopentadienyl)silane [13] and zincated (2pyridyl)methylsilane. [14] An N-heterocyclic carbene trimethylsilyl cation adduct also attacks carbon dioxide at the carbene CÀSi bond. [15,16] Theaddition of neutral organosilicon compounds to carbon dioxide often requires assistance of an excess amount of an aluminum Lewis acid [17] and fluoride.…”

RuBisCO‐inspirierte CO2‐Aktivierung und Umwandlung durch einen Iridium(I)‐Komplex

“…Dennoch weist die RuBisCO-vermittelte CO 2 -Fixierung einige interessante Aspekte auf,d eren Adaption zu neuen CO 2 -Transformationen auch durch andere Metallkomplexe führen kçnnte.E in Schlüsselaspekt ist dabei die kooperative Bindung von zwei CO 2 -Molekülen mit unterschiedlicher Funktion pro Enzym. [7] Die Tatsache,d ass die Natur auf Magnesium in diesem essenziellen Enzym setzt, scheint durch die breite Verfügbarkeit des Mg 2+ -Ions beeinflusst zu sein. (Abbildung 1b).…”

“…Dies macht Enolate und verwandte Stoffklassen wie Enamide interessant fürM odellsysteme,d ie auf solche C-C-Bindungsknüpfungen anstelle der Carbamatbildung abzielen. [7] Die Tatsache,d ass die Natur auf Magnesium in diesem essenziellen Enzym setzt, scheint durch die breite Verfügbarkeit des Mg 2+ -Ions beeinflusst zu sein. Bei der Suche nach synthetischen Metallkomplexen, die wie das natürliche Vorbild in der Lage sind, zwei CO 2 -Moleküle zu fixieren, ohne ein Protein als raffinierten multifunktionalen Liganden zu bençtigen, scheinen jedoch andere Metallionen besser ge- eignet.…”