Synthesis and Properties of a New Kinetically Stabilized Digermyne:  New Insights for a Germanium Analogue of an Alkyne

Abstract

The reduction of an overcrowded (E)-1,2-dibromodigermene, Bbt(Br)Ge=Ge(Br)Bbt (2) [Bbt = 2,6-bis[bis(trimethylsilyl)methyl]-4-[tris(trimethylsilyl)methyl]phenyl], with KC8 afforded a stable digermyne, BbtGe[triple bond]GeBbt (1). The Ge[triple bond]Ge triple-bond characters of 1 were revealed by the X-ray crystallographic analysis and spectroscopic studies (UV/vis and Raman spectra) together with theoretical calculations. The Ge[triple bond]Ge bond lengths of the two nonidentical molecules of 1 observed in the unit cell were shorter than that of the previously reported digermyne, Ar'Ge[triple bond]GeAr' (Ar' = 2,6-Dip2C6H3, Dip = 2,6-diisopropylphenyl).

Synthesis and Structure of the “Dialuminyne” Na2[Ar′AlAlAr′] and Na2[(Ar′′Al)3]: AlAl Bonding in Al2Na2 and Al3Na2 Clusters

“…The only related Group 13 element derivative of this type is the closely related compound Na 2 [Ar'GaGaAr'] (2; Ar' = C 6 H 3 -2,6-(C 6 H 3 -2,6-iPr 2 ) 2 ), which has very similar structural parameters to those of 1 but whose flanking aryl rings do not carry a para-iPr substituent. [10,11] Since 2000, however, work on the isoelectronic neutral Group 14 element derivatives RM'M'R (M' = Si, [12][13][14] Ge, [15,16] Sn, [17] Pb; [18] R = bulky organic or silyl group) has progressed to the extent that stable homonuclear species for each member of the series have now been isolated and structurally characterized. In addition, a series of related neutral Group 13 metal Ar'MMAr' derivatives (M = Ga, [10,11] In, [19] Tl [20] ) has been reported.…”

Heteroatom chemistry in Asia: Past, present, and future

“…Very recently, an aryl-substituted digermylyne was synthesized by Tokitoh et al and shown to have a Ge-Ge triple bond [28]. For this type of compound, the situation changes completely on going farther down in the periodic table.…”

Reactivity of a germa-alkyne: Evidence for a germanone intermediate in the hydrolysis and alcoholysis processes

“…for the hydrolysis and alcoholysis reactions of a digermyne [12]. The authors, using theoretical calculations, found for their Dmp model (Dmp = 2,6-dimethylphenyl) that the germanone (DmpGe(O)-GeH 2 Dmp) was 9.9 kcal/mol more stable than the enol tautomer.…”