Keywords: Density functional calculations / Electron transfer / Single electron transfer reactions / Radical ions / HSAB parametersThe reaction of 3-ferrocenyl-substituted 2H-azaphosphirene complexes 1a-c in the presence of substoichiometric amounts of ferrocenium hexafluorophosphate yields 3,5-diferrocenylsubstituted 2H-1,4,2-diazaphosphole complexes 3a-c and difluoro(organo)phosphane complexes 4a-c. The reaction of 1a,c and [FcH]PF 6 with cyanoferrocene yields 3a,c in a straightforward way. The molecular structures of 3a,c were unambiguously identified by multinuclear NMR spectroscopic experiments, mass spectrometry, and single-crystal Xray diffraction studies. DFT calculations on model complexes
Reaction of C-ferrocenyl-substituted aminocarbene tungsten complex 1 with [bis(trimethylsilyl)methylene]chlorophosphane (2) and triethylamine yielded 2H-azaphosphirene complex 3 in good yield. Reaction of complex 3 with aryl nitriles 4a-c, N-piperidinonitrile (4d), and acetonitrile (4e) in the presence of ferrocenium hexafluorophosphate yielded regioselectively 2H-1,4,2-diazaphosphole complexes 5a-e through single-electron-transfer-induced ring expansion to-
By reaction of tmp2GaCl (tmp = 2,2,6,6‐tetramethylpiperidino) (1) with dilithioferrocene the 1,1′‐digallylferrocene [{Fe(η5‐C5H4)2}(tmp2Ga)2] (2) was prepared. 2 reacted with CO2 to afford the ferrocenophane [Fe{η5‐C5H4‐Ga(O2Ctmp)(μ2‐O2Ctmp)}2] (3). Here, an eight‐membered Ga(OCO)2Ga‐Ring is the bridge in the ferrocenophane structure. The gallium carbamates [Me2GaO2Ctmp]2 (5), and tmp2Ga(η2‐O2Ctmp) (7) show structural features embedded in 3. The compounds were fully characterized by NMR, cyclovoltammetry and single crystal X‐ray structure analysis.
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