Reductive Carbonylation of [NiCl2(dippf)] (dippf = 1,1′-Bis(diisopropylphosphino)ferrocene) with Fe(CO)5 and (Spectro)electrochemistry of the Resulting [Ni(CO)2(dippf)]
datasetposted on 15.01.2019, 13:19 by Florian Döttinger, Mark R. Ringenberg
[Ni(CO)2(dippf)]  (dippf = 1,1′-bis(diisopropylphosphino)ferrocene) was synthesized from [NiCl2(dippf)] and [Fe(CO)5] at elevated temperature/pressure using microwave (MW) heating.  showed two oxidation waves in the cyclic voltammogram, and UV–vis–NIR spectroelectrochemistry (SEC) and IR SEC at −30 °C as well as computation support by means of DFT were used to determine the location and electron configuration after both oxidation events. The monocation + showed a strong NIR absorption in the UV–vis–NIR spectrum that was a IVCT [NiI → FeII] and inverse IVCT (iIVCT) [FeII → NiI], and the IR SEC spectrum of + showed multiple bands associated with two similar configurations, one where the spin is delocalized over both metal atoms and a second configuration where the spin is Ni localized. The second oxidation to 2+ occurred at the Ni atom and resulted in the formation of a Fe → Ni dative bond.