Europium is Different: Solvent and Ligand Effects on Oxidation State Outcomes and C-F Activation in Reactions Between Europium Metal and Pentafluorophenylsilver

Zhifang Guo, Victoria L. Blair, Glen B. Deacon, Peter C. Junk

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1 Citation (Scopus)

Abstract

Unique outcomes have emerged from the redox transmetallation/ protolysis (RTP) reactions of europium metal with [Ag(C6F5)(py)] (py=pyridine) and pyrazoles (RR′pzH). In pyridine, a solvent not normally used for RTP reactions, the products were mainly EuII complexes, [Eu(RR′pz)2(py)4] (RR′pz=3,5-diphenylpyrazolate (Ph2pz) 1; 3-(2-thienyl)-5-trifluoromethylpyrazolate (ttfpz) 2; 3-methyl-5-phenylpyrazolate (PhMepz) 3). However, use of 3,5-di-tert-butylpyrazole (tBu2pzH) gave trivalent [Eu(tBu2pz)3(py)2] 4, whereas the bulkier N,N′-bis(2,6-difluorophenyl)formamidine (DFFormH) gave divalent [Eu(DFForm)2(py)3] 5. In tetrahydrofuran (thf), the usual solvent for RTP reactions, C−F activation was observed for the first time with [Ag(C6F5)(py)] in such reactions. Thus trivalent [{Eu2(Ph2pz)4(py)4(thf)2(μ-F)2}{Eu2(Ph2pz)4(py)2(thf)4(μ-F)2}] (6), [Eu2(ttfpz)4(py)2(dme)2(μ-F)2] (7), [Eu2(tBu2pz)4(dme)2(μ-F)2] (8) were obtained from the appropriate pyrazoles, the last two after crystallization from 1,2-dimethoxyethane (dme). Surprisingly 3,5-dimethylpyrazole (Me2pzH) gave the divalent cage [Eu6(Me2pz)10(thf)6(μ-F)2] (9). This has a compact ovoid core held together by bridging fluoride, thf, and pyrazolate ligands, the last including the rare μ4-1η5(N2C3): 2η2(N,N′): 3κ(N): 4κ(N′) pyrazolate binding mode. With the bulky N,N′-bis(2,6-diisopropylphenyl)formamidine (DippFormH), which often favours C−F activation in RTP reactions, neither oxidation to EuIII nor C−F activation was observed and [Eu(DippForm)2(thf)2] (10) was isolated. By contrast, Eu reacted with Bi(C6F5)3 and Ph2pzH or tBu2pzH in thf without C−F activation, to give [Eu(Ph2pz)2(thf)4] (11) and [Eu(tBu2pz)3(thf)2] (12) respectively, the oxidation state outcomes corresponding to that for use of [Ag(C6F5)(py)] in pyridine.

Original languageEnglish
Article numbere202103865
Number of pages11
JournalChemistry - A European Journal
Volume28
Issue number3
DOIs
Publication statusPublished - 13 Jan 2022

Keywords

  • C−F activation
  • europium
  • pentafluorophenylsilver
  • redox transmetallation/protolysis (RTP)
  • trispentafluorophenylbismuth

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