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Here, we demonstrate that their electronic properties are in fact highly flexible and can be effectively tuned through variation of the substituent in the ylide backbone. Initial density functional theory studies showed that cyano groups are particularly capable in lowering the LUMO energy of diylidyl germylenes thus turning these usually highly nucleophilic species into electrophilic compounds. This was confirmed by experimental studies. Attempts to synthesize the germylene (Y<jats:sub>CN<\/jats:sub>)<jats:sub>2<\/jats:sub>Ge [with Y<jats:sub>CN<\/jats:sub>=Ph<jats:sub>3<\/jats:sub>P\u2010(C)\u2010CN] from the corresponding metalated ylide Y<jats:sub>CN<\/jats:sub>K selectively led to germanide [(Y<jats:sub>CN<\/jats:sub>)<jats:sub>3<\/jats:sub>Ge)K]<jats:sub>2<\/jats:sub> thus reflecting the electrophilic nature of the intermediate formed germylene. XRD analysis of single crystals of (Y<jats:sub>CN<\/jats:sub>)<jats:sub>2<\/jats:sub>Ge \u2013 serendipitously obtained through protonative cleavage of one ylide from the germanide \u2013 revealed a monomeric structure with rather long Ge\u2010ylide linkages, which corroborates well with a pure single bond and no stabilization of the empty p<jats:sub>\u03c0<\/jats:sub> orbital at germanium through \u03c0 bonding. The germanide exhibits methanide\u2010like reactivity towards chalcogens but a likewise weak Ge\u2212C bond as demonstrated by the insertion of carbon dioxide.<\/jats:p>","DOI":"10.1002\/chem.202300504","type":"journal-article","created":{"date-parts":[[2023,3,16]],"date-time":"2023-03-16T09:03:51Z","timestamp":1678957431000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":3,"title":["Inverting the Electronic Structure of Diylidylgermylenes by Backbone Modification"],"prefix":"10.1002","volume":"29","author":[{"given":"V. S. V. S. 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