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

Organogermanium Analogues of Alkenes, Alkynes, 1,3-Dienes, Allenes, and Vinylidenes

“…The first chemical evidence for the transient germyne ArGe≡CSiMe 3 [Ar = 2,6-( i Pr 2 NCH 2 ) 2 -C 6 H 3 ], generated by the low-temperature photolysis ( λ = 300 nm, −50 C°) of (diazo)germylene precursor ArGe[C(N 2 )SiMe 3 ] and trapped with t BuOH forming ArGe(O t Bu) 2 CH 2 SiMe 3 , was reported by Couret and coworkers [ 90 ]. The transient germyne ArGe≡CSiMe 3 [Ar = 2,4- t Bu-6-( i Pr 2 NCH 2 )-C 6 H 2 ] was similarly generated and trapped with water and t BuOH by Mazières and coworkers [ 91 ].…”

Gas-Phase Preparation of 1-Germavinylidene (H2CGe; X1A1), the Isovalent Counterpart of Vinylidene (H2CC; X1A1), via Non-adiabatic Dynamics through the Elementary Reaction of Ground State Atomic Carbon (C; 3P) with Germane (GeH4; X1A1)

“…The very first isolation of disilenes (SiSi) in 1981 by West et al challenged the conventional wisdom of the “double bond rule”, i.e., a postulate that main group 14 elements heavier than carbon cannot form homo- and heteronuclear multiple bonds. , As of today, stable compounds carrying homonuclear double bonds (EE, where E = Si, Ge, Sn, or Pb) − such as disilene, digermene, distannene, and diplumbene have been synthesized, and although more challenging, triply bonded compounds, including disilyne (SiSi), digermyne (GeGe), distannyne (SnSn), and diplumbyne (PbPb), were also isolated. These heavier analogues of alkynes (EE) display trans -bent geometries with decreased R–E–E angles from 137.44° (disilyne) to 94.26° (diplumbyne) and decreased bond orders from silicon to lead culminating in nearly 90° bending angles and a formal single bond in diplumbynes (RPbPbR), marking a strong contrast to acetylene and its linear geometry.…”