The production of acrylic acid (CH2CHCO2H) via homogeneous nickel-mediated coupling of ethylene (CH2CH2) and carbon dioxide (CO2) is industrially unattractive at present due to its stoichiometric, rather than catalytic, reaction profile. We utilize density functional theory (DFT) to describe the potential energy surface for both the nickel-mediated coupling reaction and an intramolecular deactivation reaction reported to hinder the desired catalytic activity. The calculated route for the catalytic production of acrylic acid can be divided into three main parts, none of which contain significantly large barriers that would be expected to prohibit the overall catalytic process. Investigation of the catalyst deactivation reaction reveals that the proposed product lies +102.6 kJ mol−1 above the reactants, thereby ruling out this type of pathway as the cause of the noncatalytic activity. Instead, it is far more conceivable that the overall reaction thermodynamics are responsible for the lack of catalytic activity observed, with the solvation -corrected Gibbs free energy of the coupling reaction in question (i.e., CH2CH2 + CO2 → CH2CHCO2H) calculated to be an unfavorable +42.7 kJ mol−1.

The supramolecular association of the previously described para-dimethylaminophenyl-substituted diorganotellurium dihalides (p-Me2NC6H4)2TeX2 (X = Cl (1), Br (2), I (3)) and (p-Me2NC6H4)RTeCl2 (R = Ph (4), p-EtOC6H4 (5)), was investigated by X-ray crystallography. Unlike almost all other structurally characterized diorganotellurium dihalides, (p-Me2NC6H4)2TeX2 (X = Cl (1), Br (2), I (3)) reveal no secondary Te∙∙∙X interactions, but X∙∙∙X interactions. The structure of (p-Me2NC6H4)PhTeCl2 (4) resembles that of Ph2TeCl2 and shows one secondary Te∙∙∙Cl contact, whereas (p-Me2NC6H4)(p-EtOC6H4)TeCl2 (5) exhibits neither secondary Te∙∙∙Cl nor Cl∙∙∙Cl interactions. The unusual structural characteristics of 1–5 are attributed to the occurrence of intermolecular Te∙∙∙π and π∙∙∙π contacts associated with quinoid π-electron delocalization across the para-dimethylaminophenyl (1–5) and para-ethoxyphenyl (5) groups.

The reaction of (p‐MeOC6H4)2TeO with two equivalents of HO3SCF3 and HO2PPh2 provided the tetraorganoditelluroxanes (F3CSO3)(p‐MeOC6H4)2TeOTe(p‐MeOC6H4)2(O3SCF3) (1) and (Ph2PO2)(p‐MeOC6H4)2TeOTe(p‐MeOC6H4)2(O2PPh2)·2 Ph2PO2H (2) in good yields. Compounds 1 and 2 were characterized by solution and solid‐state 31P and 125Te NMR spectroscopy, IR spectroscopy, electrospray mass spectrometry, conductivity measurements and single crystal X‐ray diffraction. In solution, compound 1 undergoes an electrolytic dissociation and reversibly reacts with traces of water to give the mononuclear cation [(p‐MeOC6H4)2TeOH]+ and triflate anions. Theoretical aspects of the protonation and hydration of model telluroxanes R2TeO (R = H, Me, Ph) were investigated by preliminary DFT calculations and compared to the corresponding selenoxanes R2SeO. The tellurium dihydroxides R2Te(OH)2 seem to be more stable than the hydrogen‐bonded complexes R2TeO·H2O.

Hypervalency and secondary bonding are the driving forces behind the rapid absorption of gaseous carbon dioxide by two organotellurium and organotin oxides and the unexpected formation of a unique tellurastannoxane cluster (see structure; dark red Te, black Sn, gray C, light red O). The absorption is reversible with the liberation of carbon dioxide being observed at temperatures between 90 and 145 °C.