期刊
ORGANOMETALLICS
卷 39, 期 23, 页码 4265-4272出版社
AMER CHEMICAL SOC
DOI: 10.1021/acs.organomet.0c00320
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资金
- WACKER Chemie AG
- European Research Council [SILION 637394]
By use of the ethylene-bridged bidentate bis-NHI (NHI = N-heterocyclic imine) ligand 1 toward the complexation of ECl2.(dioxane) (E = Ge, Sn) the synthesis of the first bis-NHI-stabilized chlorogermyliumylidene 2a[GeCl3] and chlorostannyliumylidene 2b[SnCl3] by Lewis base mediated autoionization was achieved. Using additional TMSOTf enabled the isolation of the corresponding triflate salts 2a[OTf] and 2b[OTf] in moderate yields. The obtained tetryliumylidene ions were fully characterized, including single-crystal Xray diffraction analysis, and additionally investigated by density functional theory calculations. Reaction of 2a[OTf] with NaBH4 led to the formation of a push-pull-stabilized hydridogermyliumylidene complex by Cl/H exchange. The same reaction with the stannyliumylidene led to transmetalation, yielding the corresponding dihydroboronium complex. Also, reactions with LiAIH(4) in both cases afforded the transmetalation product.
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