Synthesis and Application of a Perfluorinated Ammoniumyl Radical Cation as a Very Strong Deelectronator

Abstract

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.

Towards clustered carbonyl cations [M3(CO)14]2+ (M = Ru, Os): the need for innocent deelectronation

“…The comparison of [“phenazine F ”] + ˙ to the archetypical organic oxidant tris (4-bromophenyl)aminium (“magic blue”) [N(C 6 H 4 -4-Br) 3 ] + ˙ shows, that perhalogenation is needed additionally to avoid unwanted side reactions of generated cations with aromatic C–H bonds. 10 …”

“…4B ). 10 When 6 is reacted with [NO] + [F{Al(OR F ) 3 } 2 ] − in TFB (but not in o DFB), a dark green solution and evolution of gas is observed, indicating the generation of [6] + ˙ and nitrogen monoxide ( eqn (6) ). …”

“…The comparison of ["phenazine F "] +• to the archetypical organic oxidant tris(4-bromophenyl)aminium ("magic blue") [N(C 6 H 4 -4-Br) 3 ] +• shows, that perhalogenation is needed additionally to avoid unwanted side reactions of generated cations with aromatic C-H bonds. 10 Alternative Innocent Neutrals: As a potential candidate, the simplest perfluorinated arene, perfluorobenzene (benzene F ), needs extreme reagents like iridium hexafluoride for the deelectronation to its radical cation. 48 Additionally, the benzene F radical cation is highly Lewis acidic and causes the slow decomposition of the hexafluorometalate WCAs [MF 6 ] − (M = Ir, Sb) at room temperature.…”

“…Cyclovoltammetry of anthracene Hal (6) shows an electrochemically reversible half-wave potential E 1/2 at 1.42 V vs. Fc 0/+ in both 1,2-difluorobenzene (oDFB) and TFB, which is 130 mV higher than that of the previously used "phenazine F " (Figure 4B). 10 When 6 is reacted with [NO] + [F{Al(OR F ) 3 } 2 ] − in TFB (but not in oDFB), a dark green solution and evolution of gas is observed, indicating the generation of [6] +• and nitrogen monoxide (eq. 6).…”

“…8 The prediction is even less straight forward for heteroleptic TMCCs: An illustrative example is [(Cp*) 2 Fe-CO] 2+ , which bears iron in the formal oxidation state +IV, but is a classical carbonyl complex. 9,10 Hence, the investigation of novel homoleptic TMCCs remains an interesting field with potential for new discoveries, despite the fact that meanwhile the monometallic TMCCs of many transitions metals were already isolated in condensed phases. 2,7,11 Still, the weak interaction of carbon monoxide with metal cations requires the strict absence of other nucleophiles, which implies the use of both, weakly coordinating anions (WCAs) and weakly coordinating solvents / media.…”