Inorganic Chemistry, Vol.53, No.13, 6482-6490, 2014
Reaction Mechanisms of Small-Molecule Activation by Amidoditetrylynes R2N-EE-NR2 (E = Si, Ge, Sn)
The calculated reaction profiles using density functional theory at the BP86/TZVPP level for the reaction of small molecules with amidoditetrylynes R2N-EE-NR2 (E = Si, Ge, Sn) are discussed. Four projects are presented that feature the virtue of cooperation between theory and experiment. First, the calculated reaction paths for hydrogenation of the model systems (Me2N)EEL(NMe2) (E = Si, Ge, Sn), which possess E-E single bonds, are examined. The results for the germanium model systems are compared with hydrogenation of the real system (LGeGeL dagger)-Ge-dagger where L-dagger = NAr*(SiMe3) (Ar* = C6H2{C(H)Ph-2}(2)Me-2,6,4). The second project introduced the multiply bonded amidodigermyne (LGeGeL dagger dagger)-Ge-dagger dagger, which carries the extremely bulky substituents L-dagger dagger = N(Ar-dagger dagger)(SiPr3i), where Ar-dagger dagger = C6H2{C(H)Ph-2}(2)Pr-i-2,6,4. The theoretical reaction profile for dihydrogen addition to (LGeGeL dagger dagger)-Ge-dagger dagger is discussed. Hydrogenation gives L-dagger dagger(H)GeGe(H)L-dagger dagger as the product, which is in equilibrium with the hydrido species Ge(H)L-dagger dagger. The latter germanium hydride and tin homologue Sn(H)L-dagger dagger were found to be effective catalysts for hydroboration reactions, which is the topic of the third project. Finally, the calculated reaction course for the reduction of CO2 to CO with the arnidodigermyne LtGeGeLt is discussed.