Exploring the Synthesis and Coordination Chemistry of Pentafluorophenylcopper: Organocopper Polyanions and Coordination Networks

Abstract

Cu-C6F5]4 is a thermally stable and soluble compound with suitable reactivity for synthetic applications in organic and inorganic chemistry. Here the synthesis of [Cu-C6F5]4 is explored in different solvents and followed by in-situ 19 F NMR spectroscopy. The importance of solvent choice during the synthesis from Grignard reagent C6F5MgBr is highlighted, with a range of magnesium cuprate species identified and isolated when THF is used as solvent (rather than Et2O), including [Cu(C6F5)2]and the remarkable organocopper polyanion ([Cu5(C6F5)7] 2-)∞. The coordination chemistry of [Cu-C6F5]4 with 1,4-dioxane is investigated in solution and in the solid state, with an extended coordination network, [Cu-C6F5]4(dioxane), structurally resolved for the first time. This structure reveals interwoven linear and zig-zag chains featuring dioxane donors unusually coordinating to adjacent Cu sites of some of the [Cu-C6F5]4 tetramers.

Real‐Time In Situ Volatile Organic Compound Sensing by a Dual‐Emissive Polynuclear Ln‐MOF with Pronounced LnIII Luminescence Response

“…One feature they have in common is that their relatively high ring tension makes O lone pairs more exposed for binding with metal ions. [58][59][60][61][62] Given the presence of the "binding pocket", three THF/1,4-dioxane molecules are preferentially trapped within the channel window and coordinate to Eu 9 clusters by competitively substituting three equatorial H 2 O ligands (Figures 3 and S18). Not only shielding the OH quencher from the first coordination sphere of Eu 3 + , these coordinated analytes are also well poised for subsequent linkage with the free ones by defining a more confined space.…”

“…Among the analytes, THF and 1,4‐dioxane are two cyclic ethers with a five‐ and six‐membered ring structure, respectively. One feature they have in common is that their relatively high ring tension makes O lone pairs more exposed for binding with metal ions [58–62] . Given the presence of the “binding pocket”, three THF/1,4‐dioxane molecules are preferentially trapped within the channel window and coordinate to Eu 9 clusters by competitively substituting three equatorial H 2 O ligands (Figures 3 and S18).…”

Adamantane-type clusters: compounds with a ubiquitous architecture but a wide variety of compositions and unexpected materials properties

“…[µ4-O{Cu(MeOH)}4Cl6-nBrn] (780-786), OPPh3 / MeOH, 60 °C, 6 h Q [456,457] HMTA = Hexamethylentetramine, HBDA = Hexakis (808, dpipa = N,N'dimethylpiperazine), obtained from dissolving elemental Cu in HCl together with dpipa and treating it solvothermally in queous solution at 120 °C degree for 24 h. [459] The analogous Br cluster [Cu4Br6] 2− (in 809-816) is found in combination with different ammonium, phosphonium and a Mg complex counterions, always available through a reaction of CuBr with the corresponding complex bromide. [460][461][462][463][464] One such cluster (806) was also found in a side reaction during the catalytical C-C bond formation between allyl bromide and a (C6F5) − ligand from a mixed Cu/Al complex. [465] The congener of [466,467] There is only one example of a compound with a [Cu4Br6] inorganic core carrying terminal ligands: [{Cu(Hdabco)}4Br6](HCOO)2 (817, dabco = 1,4diazabicyclo[2.2.2]octane).…”

“…[483][484][485] In these compounds, each Al site carries three terminal fluorine ligands. CuBr, MgBr2 / THF, 50 °C, 18 h C [464] [(Poxim)2AlBr][Cu4Br6] (814) [Al(C6F5)3(toluene)0.5], CuO t Bu, Poxim, allyl bromide, C14H30 / toluene, −30 °C to 80 °C, 7 h, U [465] (H2dpipa)3[Cu4Br6][Cu2Br6] (815) Cu, HBr, dpipa / 180 °C, 24 h B [459,467] CuI, LiI, benzo-15-crown-5, ascorbic acid / H2O, Me2CO, reflux, 4 h C [475] [Cs(benzo-15-crown-5)]2[Cu4I6] (825) CuI, CsI, benzo-15-crown-5, ascorbic acid / H2O, Me2CO, reflux, 2 h C [475] [Na(18-crown-6)H2O]2(H2O)[Cu4I6] (826) CuI, NaI, 18-crown-6, ascorbic acid / H2O, Me2CO, reflux, 6 h C [475] [Rb(18-crown-6)]2(MeCN)[Cu4I6] (827) RbI, Cu, [NH4]I, 18-crown-6 / MeCN, 60 °C, 28 h C [476] [Mn(tdpmO3)2][Cu4I6] (828) CuI, MnI2, tdpmO3 / MeCN, 30 min C [477] [Mn(dppbO2…”

“…456,457 459 The analogous Br cluster [Cu 4 Br 6 ] 2− (in 809-816) is found in combination with different ammonium, phosphonium and a Mg complex counterions, always available through a reaction of CuBr with the corresponding complex bromide. [460][461][462][463][464] One such cluster (806) was also found in a side reaction during the catalytical C-C bond formation between allyl bromide and a (C 6 F 5 ) − ligand from a mixed Cu/Al complex. 465 The congener of the only known Cl species discussed before [H 2 466,467 There is only one example of a compound with a [Cu 4 Br 6 ] inorganic core carrying terminal ligands: [{Cu(Hdabco)} 4 Br 6 ](-HCOO) 2 (817, dabco = 1,4-diazabicyclo[2.2.2]octane).…”