{"database":"biostudies-literature","file_versions":[],"scores":null,"additional":{"submitter":["Uchida D"],"funding":["Japan Science and Technology Agency","Japan Society for the Promotion of Science"],"pagination":["22597-22602"],"full_dataset_link":["https://www.ebi.ac.uk/biostudies/studies/S-EPMC12560044"],"repository":["biostudies-literature"],"omics_type":["Unknown"],"volume":["16(47)"],"pubmed_abstract":["We report the synthesis of the first neutral homoaromatic heavy allene, stabilized by a methylene-bridged four-membered framework. Single-crystal X-ray diffraction and DFT calculations reveal a cyclic three-center-two-electron (3c-2e) π interaction, a short bridgehead distance, a delocalized HOMO, and a strongly negative NICS(-1) value (-16.9 ppm), collectively establishing pronounced homoaromaticity. Coordination of 4-dimethylaminopyridine (DMAP) induces a clean and selective transformation into a germylene-coordinated digermavinylidene, without substituent migration. This reactivity originates from LUMO localization at the bridgehead Ge atom supported by Wiberg bond indices and NBO analyses. Our findings highlight neutral homoaromaticity as a structural platform for programmable bonding "],"journal":["Chemical science"],"pubmed_title":["A neutral homoaromatic heavy allene as a platform for selective conversion to a germylene-coordinated digermavinylidene."],"pmcid":["PMC12560044"],"funding_grant_id":["JPMJFS2123","JP18H01963","JP25H02026","JP24K01496"],"pubmed_authors":["Mizuhata Y","Yamada H","Uchida D"],"additional_accession":[]},"is_claimable":false,"name":"A neutral homoaromatic heavy allene as a platform for selective conversion to a germylene-coordinated digermavinylidene.","description":"We report the synthesis of the first neutral homoaromatic heavy allene, stabilized by a methylene-bridged four-membered framework. Single-crystal X-ray diffraction and DFT calculations reveal a cyclic three-center-two-electron (3c-2e) π interaction, a short bridgehead distance, a delocalized HOMO, and a strongly negative NICS(-1) value (-16.9 ppm), collectively establishing pronounced homoaromaticity. Coordination of 4-dimethylaminopyridine (DMAP) induces a clean and selective transformation into a germylene-coordinated digermavinylidene, without substituent migration. This reactivity originates from LUMO localization at the bridgehead Ge atom supported by Wiberg bond indices and NBO analyses. Our findings highlight neutral homoaromaticity as a structural platform for programmable bonding ","dates":{"release":"2025-01-01T00:00:00Z","publication":"2025 Dec","modification":"2026-07-15T13:26:51.118Z","creation":"2026-07-05T03:08:18.251Z"},"accession":"S-EPMC12560044","cross_references":{"pubmed":["41164305"],"doi":["10.1039/d5sc07177a"]}}