Hydrogermolysis reactions involving the α-germylated nitriles R3GeCH2CN (R=Ph, Pri, But) and germanium amides R3GeNMe2 (R=Pri, But) with Ph3GeH: Substituent-dependent reactivity and crystal structures of Pri3GeGePh3 and But3Ge[NHC(CH3)CHCN]

Reaction of germanes and digermanes with triflic acid: The route to novel organooligogermanes

“…At the action of two equivalents of HOTf on the hexaphenyldigermane (5) the new complex (OTf)Ph 2 GeGePh 2 (OTf) (7) was obtained with high yield (Scheme 3).…”

Gas Source Techniques for Molecular Beam Epitaxy of Highly Mismatched Ge Alloys

“…Moreover, the central carbon atom is also sterically protected by the bulky germanium atoms as in compound 1 (covalent radii: C = 0.77 Å, Ge = 1.22 Å) [43] (see Figure 2) thus assisting in driving the dissociation of the stronger Ge-H bonds [18]. Indeed, this is the case for hydrogermolysis reactions where the stronger terminal Ge-H bond in R 3 Ge-H (R = Ph, Me) is cleaved at slightly elevated temperatures in preference to the weaker Ge-C bonds forming a Ge-Ge bond (256 kJ/mol) in R 3 Ge-GeR' 3 (R = Ph, R' = Et, Bu, Ph; R = Me, R' = Bu) [34,46,47]. Hence, we proceeded in attempting to reproduce the syntheses of (H 3 Ge) 4 C by utilizing lithium aluminium hydride to hydrogenate 4GeMe.…”

Synthetic, Structural, and Physical Aspects of Organo-Oligogermanes

“…The reason for the success of this process is the fact that the germanium amide reacts with the CH 3 CN solvent to generate an a-germyl nitrile, which has a labile Ge -C bond and is the active species in the Ge -Ge bond forming process, as illustrated for the synthesis of Ph 3 GeGePh 3 in Scheme 5. [69,70] Therefore, the acetonitrile is not only the solvent but also a reagent in this process. We have unequivocal evidence for the reaction pathway, as the a-germyl nitrile Ph 3 GeCH 2 CN can be prepared independently from Ph 3 GeCl and LiCH 2 CN (Scheme 5) and isolated, and this material subsequently reacts with Ph 3 GeH to generate the digermane.…”

“…A resonance at d 2.08 ppm increased in intensity as the reaction proceeded and this feature matched exactly with that for a sample of CH 3 CN in CD 3 CN solvent. [70] We found that the a-germyl nitrile reagents were not stable for long periods of time, even when stored under N 2 at À35 C. This, and the greater complexity involved in preparing these reagents, resulted in our using the germanium amide reagent as starting materials such that the a-germyl nitriles are typically generated in situ and are not isolated. We attempted the hydrogermolysis reaction in other reaction media and no reaction was observed.…”

“…[6,8,[69][70][71] This is a powerful synthetic method, since it allows for variation of not only the length of the Ge -Ge backbone but also for the variation of the identity of the organic substituents attached to the GeGe chain. The latter feature is uncommon for synthetic methods used to generate oligogermane species, and many of the compounds reported prior to our initial investigations had identical substituents attached to each of the germanium centers.…”