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A Germacalicene: Synthesis, Structure, and Reactivity
Author(s) -
Dong Zhaowen,
Albers Lena,
Schmidtmann Marc,
Müller Thomas
Publication year - 2019
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201805258
Subject(s) - cationic polymerization , reactivity (psychology) , chemistry , dimer , perchlorate , nucleophile , ylide , crystal structure , medicinal chemistry , crystallography , polymer chemistry , organic chemistry , catalysis , ion , medicine , alternative medicine , pathology
The synthesis of the germacalicene 7 from the reaction of the dipotassium germole dianion K 2 [ 6 ] with 1,2‐bis‐diisopropylamino‐3‐chlorocyclopropenyl perchlorate is reported. Based on the crystal structure analysis and the results of DFT calculations, the germacalicene 7 can be viewed as a cyclopropenium germacyclopentadienide ylide that is isoelectronic to α‐cationic phosphanes. First reactivity studies revealed its nucleophilic character and resulted in the isolation of the air‐ and moisture‐stable carbonyl iron complex 15 and the cationic silver complex 20 . One‐electron oxidation of the germacalicene 7 was achieved by its reaction with [Ph 3 C][B(C 6 F 5 ) 4 ] and the bis‐cationic Ge−Ge‐bonded dimer 22 was isolated.