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Synthesis and reactivity of a germylene stabilized by a boraguanidinate ligand
Authors: Böserle Jiří | Alonso Mercedes | Jambor Roman | Růžička Aleš | Dostál Libor
Year: 2016
Type of publication: článek v odborném periodiku
Name of source: RSC Advances
Publisher name: Royal Society of Chemistry
Place: Cambridge
Page from-to: 19377-19388
Titles:
Language Name Abstract Keywords
cze Syntéza a reaktivita germylénu stabilizovaným boraguanidinatovým ligandem Byl připraven germylene [(i-Pr)(2)NB(N-2,6-Me2C6H3)(2)]Ge (1) reakci dilitné soli [(i-Pr)(2)NB(N-2,6-Me2C6H3)(2)]Li-2 s GeCl2. Reakce této sloučeniny byly dále studovány.
eng Synthesis and reactivity of a germylene stabilized by a boraguanidinate ligand The germylene [(i-Pr)(2)NB(N-2,6-Me2C6H3)(2)]Ge (1) was easily accessible by the reaction of the in situ prepared dilithium precursor [(i-Pr)(2)NB(N-2,6-Me2C6H3)(2)]Li-2 with GeCl2 dioxane complex. The bonding situation in 1 has been also described from the theoretical point of view. This germylene is smoothly oxidized by diphenyldichalcogenides PhEEPh, I-2 or Mel to produce bis(phenylchalcogenato)germanes [(i-Pr) 2NB(N-2,6-Me2C6H3) (2)] Ge(EPh)(2) [where E = S (2), Se (3) and Te (4)] and corresponding iodo-derivatives [(i-Pr)(2)NB(N-2,6-Me2C6H3)(2)]GeI2 (5) and [(i-Pr)(2)NB(N-2,6-Me2C6H3)(2)] Ge(Me)I (6). The treatment of 1 with bromine resulted in the unexpected formation of a heteroleptic germylene compound [(i-Pr)(2)NB(NH-2,6-Me2C6H3)(N-2,6-Me2C6H3)]GeBr (7) and a germanium(IV) compound [(i-Pr) 2NB(NH-2,6-Me2C6H3)(N-2,6-Me2C6H3)]GeBr3 (8). The reaction of germylene 1 with 2,3-dimethylbutadiene and 2,3-dibenzylbutadiene resulted in spiro-compounds [(i-Pr)(2)NB(N-2,6-Me2C6H3)(2)] Ge[CH2C(R)=C(R)CH2] [where R = Me (10) and benzyl (11)]. Similarly, compound [(i-Pr)(2)NB(N-2,6-Me2C6H3) (2)] Ge[N(Dip)CH=CHN(Dip)] (12) (where Dip = 2,6-i-Pr2C6H3) was obtained by the reaction of 1 with corresponding diimine (Dip) N] CHCH] N(Dip). All compounds were characterized by multinuclear NMR spectroscopy and their molecular structures were unambiguously established using single-crystal X-ray diffraction analysis. x-ray structures; n-heterocyclic germylene; bond covalent radii; correlated molecular calculations; heavier carbene analogs; gaussian-basis sets; c-h activation; cyclic diazastannylenes; oxidative addition; triple-bond

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