The perfluorinated dihydrophenazine derivative (perfluoro‐5,10‐bis(perfluorophenyl)‐5,10‐dihydrophenazine) (“phenazineF”) can be easily transformed to a stable and weighable radical cation salt by deelectronation (i.e. oxidation) with Ag[Al(ORF)4]/ Br2 mixtures (RF=C(CF3)3). As an innocent deelectronator it has a strong and fully reversible half‐wave potential versus Fc+/Fc in the coordinating solvent MeCN (E°′=1.21 V), but also in almost non‐coordinating oDFB (=1,2‐F2C6H4; E°′=1.29 V). It allows for the deelectronation of [FeIIICp*2]+ to [FeIV(CO)Cp*2]2+ and [FeIV(CN‐tBu)Cp*2]2+ in common laboratory solvents and is compatible with good σ‐donor ligands, such as L=trispyrazolylmethane, to generate novel [M(L)x]n+ complex salts from the respective elemental metals.

Supporting information (experimental details, procedures, weights, 1D-and 2D-NMR spectra, IR spectra and powder diffraction patterns of the reactions, details to the quantum chemical calculations and crystallographic details) and the ORCID identification number(s) for the author(s) of this article can be found under: https://doi.

A stable salt of the metalloradical [Ni(C 6 H 6 ) 2 ] + hitherto unknown in the condensed phase was synthesized from [Ni(CO) 4 ] + [WCA] À and benzene. Single crystal XRD reveals a remarkable asymmetrically η 3 ,η 6slipped sandwich structure. The magnetic properties of the [Ni(C 6 H 6 ) 2 ] + cation were determined in solution and in the gas phase. Oxidation with the synergistic Ag + / 0.5 l 2 system led to the salt [Ni(C 6 H 6 ) 2 ] 2 + ([WCA] À ) 2 . All products were fully characterized by means of IR, Raman, NMR/EPR, single crystal and powder XRD.

Although the discovery of the Ga(I) complex salt [Ga(PhF)2‐3][Al(ORF)4] (RF = C(CF3)) invoked the preparation of a diverse library of cationic Ga(I) coordination complexes and clusters, studies on small molecule activation with low‐valent Ga(I) cations are scarce. Here, a first experimental study on the reactivity of a monomeric Ga(I) cation activated with a pyridine‐diimine pincer‐ligand (in [Ga(PDIdipp)][Al(ORF)4]) towards small‐molecules is reported. First controlled oxidative additions of the Ga(I) cation into C−Cl, H−P and P−P bonds are presented. Moreover, the [4+1] cycloaddition to butadienes was achieved. Intriguingly, the isolated, blue insertion product into the P−P bond of P4 allows for quantitative release of the P4 molecule upon reaction with AlEt3 and butadienes. Reversible P4 insertion of main‐group metals has previously on been reported for Ge and Sn respectively. The experimental study is supported by high level computational analysis of the in part reversible oxidative additions at the DLPNO‐CCSD(T)/def2‐TZVPP//PBEh‐3c/def2‐mSVP level of theory with COSMO‐RS solvation in 1,2‐difluorobenzene.

The stable, easily accessible salt [Ni(CO)4]+[F{Al(ORF)3}2]− (RF=C(CF3)3) was used as a NiI synthon to generate the novel half‐sandwich complexes [Ni(arene)(CO)2]+ (arene=C6H6, o‐dfb=1,2‐F2C6H4). By irreversible removal of CO from the equilibrium, even the rather endergonic reaction to a [Ni(o‐dfb)2]+ salt was successful (ΔrG°(solv)=+78 kJ mol−1). The latter displays an unprecedented slipped η3,η3‐sandwich structure and is the ultimate synthon to NiI‐chemistry.