%0 Journal Article %T Synthesis and Electrochemical Study of 1,1′-Thienyl-Substituted Fused Bis-germatranes with a Core 5c-6e Hyperbond %+ Latvian Institute of Organic Synthesis [Riga, Lituania] %+ Institut des Sciences Chimiques de Rennes (ISCR) %A Romanovs, V. %A Spura, J. %A Jouikov, V. %Z REGPOT-CT-2013-316149-InnovaBalt, European Commission 7th Framework Program %Z 39660QC, OSMOSE %< avec comité de lecture %@ 0039-7881 %J Synthesis: Journal of Synthetic Organic Chemistry %I Georg Thieme Verlag %V 50 %N 18 %P 3679-3685 %8 2018-09 %D 2018 %R 10.1055/s-0037-1610180 %K bis-germatranes %K cation radicals %K electrochemical oxidation %K hyperbonds %Z Chemical SciencesJournal articles %X Novel fused bis-germatranes containing three hypercoordinated atoms (two Ge and one N) and substituted at the 1,1′-positions with bromo-thienyl groups [(3-bromo-2-thienyl)-, (3,5-dibromo-2-thienyl)-, and 3-(4-bromo)-2-thienyl] have been synthesized from the corresponding triethoxy(thienyl)germanes and tris(1,3-dihydroxypropan-2-yl)amine. The doubly degenerated HOMO and HOMO-1 in these compounds are localized on the thienyl substituents while a 5c-6e hyperbond of the bis-germatranyl core (C-Ge←N→Ge-C system) is only a lower lying HOMO-2. Square-wave pulse voltammetry in CH 3 CN/0.1 M Bu 4 NPF 6 shows all three compounds to undergo reversible electrochemical oxidation affecting one thienyl substituent. The DFT B3LYP/Lanl2DZ//HF/6-311G(d,p) calculations of their cation radicals suggest the enhancement and shortening of the N→Ge intramolecular dative bond on the side of the oxidized thienyl unit because of the positive charge and the increased acceptor character of the latter; this is accompanied by the loss of the N→Ge dative bond on the side of the non-oxidized substituent and a substantial pyramidalization of the Ge atom. © Georg Thieme Verlag Stuttgart. New York. %G English %L hal-01881063 %U https://univ-rennes.hal.science/hal-01881063 %~ UNIV-RENNES1 %~ CNRS %~ INSA-RENNES %~ ENSC-RENNES %~ OPENAIRE %~ ISCR %~ SCR_CPM %~ STATS-UR1 %~ UR1-SPM %~ INC-CNRS %~ UR1-UFR-SPM %~ UR1-HAL %~ ISCR-CORINT %~ UR1-SDLM %~ TEST-UR-CSS %~ UNIV-RENNES %~ INSA-GROUPE %~ ISCR-CORINT2 %~ TEST-HALCNRS %~ UR1-MMS %~ ISCR-CORINT3 %~ TEST2-HALCNRS