1,16‐Di‐tert‐butyl‐1,16‐diphospha[5.5]ferrocenophane was prepared in 76% yield by deprotonation of 1,1’‐di(2‐tert‐butylphosphanylethyl)ferrocene followed by treatment with 1,1’‐di(2‐bromoethyl)ferrocene. The ferrocenophane exists as a mixture of syn and anti diastereomers, which were separated by repeated precipitation of one of them. Reaction with borane afforded the respective borane adducts in 47% yield. Methylation with iodomethane gave the respective diphosphonium salt in quantitative yield. Oxidation with 1.0 or 5.0 equivalents of silver hexafloroantimonate gave a green and a blue material, respectively, presumably the mono and the diferrcenium salts. 1,16‐Di‐tert‐butyl‐1,16‐diphospha[5.5]ferrocenophane and its oxidation products were subjected to a temperature‐dependent Mössbauer effect (ME) study to elucidate their dynamical and paramagnetic relaxation characteristics. The ME data are consistent with the absence of spin averaging for the two distinct Fe sites in the monooxidation product over the temperature range 91
In continuation of our research in cyclopentadienylalkylphosphane nickel chelates with secondary phosphane tethers the first cationic representatives of this class of compounds are reported. These were obtained by reaction of the respective bromo complex with tris(4-trifluoromethylphenyl)phosphane as well as with a number of alkyl and aryl isonitriles in the presence of indium tribromide. This Lewis acid is crucial for the success of the reactions leading to the respective tetrabromoindate salts. The compounds were characterized spectroscopically, including rare 14 N, 13 C couplings being observed. Finally, deprotonation experiments are reported, which provide some evidence for deprotonation taking place, although the expected phosphinidene chelates could not be isolated due to rapid decomposition.
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