biostudies-literatureHe ZAdvanced Research Center - Chemical Building Blocks ConsortiumDutch Research Council (NWO)National Natural Science Foundation of ChinaShanghaiTech University11725-11733https://www.ebi.ac.uk/biostudies/studies/S-EPMC9377512biostudies-literatureUnknown61(30)In this paper, we report the synthesis of a unique silicon(I)-based metalla-disilirane and report on its reactivity toward TMS-azide and benzophenone. Metal complexes containing disilylenes ((bis)silylenes with a Si-Si bond) are known, but direct ligation of the Si(I) centers to transition metals always generated dinuclear species. To overcome this problem, we targeted the formation of a mononuclear iron(0)-silicon(I)-based disilylene complex via templated synthesis, starting with ligation of two Si(II) centers to iron(II), followed by a two-step reduction. The DFT structure of the resulting η²-disilylene-iron complex reveals metal-to-silicon π-back donation and a delocalized three-center-two-electron (3c-2e) aromatic system. The Si(I)-Si(I) bond displays unusual but well-defineInorganic chemistryReactivity of a Unique Si(I)-Si(I)-Based η²-Bis(silylene) Iron Complex.PMC937751221801166OCENW.KLEIN.1932018.015.CYan KKrogman Jde Zwart FJvan der Vlugt JILiu LHe ZDemeshko Sde Bruin BEhlers AWXue XfalseReactivity of a Unique Si(I)-Si(I)-Based η²-Bis(silylene) Iron Complex.In this paper, we report the synthesis of a unique silicon(I)-based metalla-disilirane and report on its reactivity toward TMS-azide and benzophenone. Metal complexes containing disilylenes ((bis)silylenes with a Si-Si bond) are known, but direct ligation of the Si(I) centers to transition metals always generated dinuclear species. To overcome this problem, we targeted the formation of a mononuclear iron(0)-silicon(I)-based disilylene complex via templated synthesis, starting with ligation of two Si(II) centers to iron(II), followed by a two-step reduction. The DFT structure of the resulting η²-disilylene-iron complex reveals metal-to-silicon π-back donation and a delocalized three-center-two-electron (3c-2e) aromatic system. The Si(I)-Si(I) bond displays unusual but well-define2022-01-01T00:00:00Z2022 Aug2025-04-25T19:05:33.986Z2025-02-19T04:10:43.849ZS-EPMC93775123585741310.1021/acs.inorgchem.2c01369