The Facile Reduction of Carbon Dioxide to Carbon Monoxide with an Amido‐Digermyne

Abstract

Taking the fizz out: A digermyne compound with a Ge-Ge single bond has been shown to quantitatively reduce CO(2) to CO at temperatures as low as -40 °C. The mechanism of this unprecedented reaction has been probed by spectroscopic and computational techniques and involves a metastable intermediate (see picture; Ar*=C(6) H(2){C(H)Ph(2)}(2)Me-2,6,4).

Mechanistic Study of Stepwise Methylisocyanide Coupling and C–H Activation Mediated by a Low-Valent Main Group Molecule

“…Adduct formation is often an initial step in the reaction of main group species with unsaturated molecules, and synergistic interactions between main group species and the frontier orbitals of the ligand propagate further reaction. 36 The infra-red spectrum of 1 shows a slight shift of the C-N stretching band to higher frequency (2165 cm -1 ) in comparison to the free isocyanide (cf. 2161 cm -1 ), indicative of n → π* back-bonding between the germanium(II) lone pair and the π* orbital of the isocyanide ligand.…”

Reaction Mechanism of the Symmetry‐Forbidden [2+2] Addition of Ethylene and Acetylene to Amido‐Substituted Digermynes and Distannynes Ph2NEENPh2, (E=Ge, Sn): A Theoretical Study

“…[13] Experimental studies showed that amido-digermynes are very reactive also with other molecules such as CO 2 and isonitrile tBuNC. [14] Note that Ar'GeGeAr' cannot reduce tBuNC, [15] suggesting again that amido-digermynes are more reactive than their aryl congeners. In av ery recent study,J ones and coworkers found that the amido-digermynes also reactw ithv arious unsaturated substrates, such as olefins, dienes,a lkynes, and PhNNPh.…”

Stabilization of Silicon–Carbon Mixed Oxides

“…Notably, the CO 2 -mediated insertions of oxygen (and CO 3 ) into the Si−Si and Ge−Ge single bonds have been observed in the synthesis of 6 and 8, respectively (Scheme 1). 26,27 In contrast to 2, reaction of carbene-stabilized Si 2 O 4 (3) with CO 2 only resulted in immediate decomposition, giving L:CO 2 as the only characterized byproduct. Moreover, reaction of either 1 or 2 with excess CO 2 , or combining 4 with CO 2 , only gave the L:CO 2 adduct and uncharacterized silicon−carbon-based oxide powder, suggesting the importance of controlling the amount of CO 2 added to the reaction system.…”