Ni(CO) 2 (dippf)] [1] (dippf = 1,1′-bis-(diisopropylphosphino)ferrocene) was synthesized from [NiCl 2 (dippf)] and [Fe(CO) 5 ] at elevated temperature/pressure using microwave (MW) heating. [1] 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 [1] + showed a strong NIR absorption in the UV−vis−NIR spectrum that was a IVCT [Ni I → Fe II ] and inverse IVCT (iIVCT) [Fe II → Ni I ], and the IR SEC spectrum of [1] + 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 [1] 2+ occurred at the Ni atom and resulted in the formation of a Fe → Ni dative bond.
[Ni(CO)2(dppf)] [1] {dppf = 1,1′‐bis(diphenylphosphino)ferrocene} was made by reductive carbonylation of [NiCl2(dppf)] with [Fe(CO)5], similar to our recent report in Organometallics, 2019, 38, 586–592. Complex [1] showed two oxidation waves in the cyclic voltammogram. UV/Vis‐NIR spectroelectrochemistry (SEC) and IR SEC at –30 °C as well as computational support by means of DFT was used to assign the oxidation state of both metal atoms after oxidation. The monocation [1]+ showed a strong NIR absorption band which was described as an IVCT [NiI→FeII] and inverse IVCT (iIVCT) or hole transfer [FeII→NiI] based on time dependence DFT (TD‐DFT). The IR SEC spectrum of [1]+ showed multiple bands associated with two similar configurations, one which had the spin delocalized over both metal atoms and a second configuration where the spin is primarily Ni localized. The second oxidation to [1]2+ occurred at the Ni atom and resulted in release of a CO ligand followed by the formation of dimeric complex determined by low temperature IR SEC.
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