Condensation of 1,4-dimethoxybenzene (DMB) with paraformaldehyde in the presence of BF3.O(C2H5)2 gave novel para-bridged pentacyclic pillar DMB (DMpillar[5]arene). Moreover, para-bridged pentacyclic hydroquinone (pillar[5]arene) was prepared. Pillar[5]arene formed 1:1 host-guest complexes with dialkyl viologen and alkyl pyridinium derivatives. However, pillar[5]arene did not form complexes with the diadamantyl viologen derivative since a bulky adamantyl group was unable to thread the cavity of pillar[5]arene.
A series of pillar[5]arene derivatives with alkyl groups of different length were synthesized. The new alkyl-substituted pillar[5]arene derivatives 1,4-bis(ethoxy)pillar[5]arene (C2), 1,4-bis(propoxy)pillar[5]arene (C3), 1,4-bis(butoxy)pillar[5]arene (C4), 1,4-bis(pentyloxy)pillar[5]arene (C5), 1,4-bis(hexyloxy)pillar[5]arene (C6), and 1,4-bis(dodecanoxy)pillar[5]arene (C12) were obtained by Lewis acid-catalyzed condensation of dialkoxybenzene monomers with paraformaldehyde. The conformational characteristics of the pillar[5]arene derivatives were investigated by dynamic (1)H NMR measurements. When the alkyl substituents were bulkier than methyl groups, the rotation of phenolic units in the pillar[5]arenes was suppressed and their conformation was immobilized. As their length increased, the alkyl substituents packed at the upper and lower rims and thus lowered the conformational freedom of the pillar[5]arenes.
A six-coordinate bis(μ-oxo)nickel(III) complex, [Ni2(μ-O)2(Me3-tpa)2]2+ (1), was synthesized by
the reaction of [Ni2(μ-OH)2(Me3-tpa)2]2+ (2) with 1 equiv of hydrogen peroxide in methanol at −90 °C, where
Me3-tpa = tris(6-methyl-2-pyridylmethyl)amine. The 6-methyl groups of Me3-tpa have a significant influence
on the formation and stabilization of the high-valent bis(μ-oxo)dinickel(III) species. The reaction of 2 with a
large excess of hydrogen peroxide (>10 equiv) afforded a novel bis(μ-superoxo)dinickel(II) complex, [Ni2(μ-O2)2(Me3-tpa)2]2+ (3), thus, the reaction demonstrates a unique conversion of a NiIII(μ-O)2NiIII core into a
NiII(μ-OO)2NiII core upon exposure to hydrogen peroxide. Complexes 1, 2, and 3 have been characterized by
X-ray crystallography and various physicochemical techniques. Complex 1 has a Ni(μ-O)2Ni core and the
average Ni−O and Ni−N bond distances (1.871 and 2.143 Å, respectively) are significantly shorter than those
of 2 (2.018 and 2.185 Å, respectively), suggesting that 1 is a bis(μ-oxo)dinickel(III) complex. Complex 3
consists of a Ni(μ-OO)2Ni core with two μ-1,2-O−O bridges to form a six-membered ring with chair
conformation and the O−O bond distance is 1.345(6) Å. The resonance Raman spectrum of a powdered sample
of 3 measured at ∼110 K showed an isotope-sensitive band at 1096 cm-1 (1044 cm-1 for an 18O-labeled
sample), indicating that 3 is a bis(μ-superoxo)dinickel(II) complex. Thermal decomposition of both 1 and 3 in
acetone at −20 °C under N2 atmosphere resulted in partial hydroxylation of a methyl group of Me3-tpa in
yields of 21−27% for both complexes. For complex 3, a carboxylate complex, [Ni(Me2-tpaCOO)(OH2)]+ (4),
where one of the three methyl groups of Me3-tpa is oxidized to carboxylate, was also isolated as a decomposed
product under N2 atmosphere. During the decomposition process of 3, dioxygen evolution was simultaneously
observed. The electrospray ionization mass spectrometry (ESI-MS) of 3 revealed the formation of 1 during
the decomposition process. These results suggest that one possible decomposition pathway of 3 is a
disproportionation of two coordinated superoxides to dioxygen and peroxide followed by the O−O bond scission
of peroxide to regenerate 1, which is responsible for the hydroxylation and the oxidation of the 6-methyl
group of Me3-tpa.
We monitored the progress of formation of dimethoxypillar[5]arene by size-exclusion chromatography. Surprisingly, the cyclization reaction completely finished in just 3 min. By improving the reaction conditions and purification process, we successfully obtained dimethoxypillar[5]arene in a short time and in high yield (71%) from commercially available reagents. By improving the deprotection reaction of the methoxy moieties, pillar[5]arene was isolated quantitatively. Single crystal X-ray analysis confirmed the structure of pillar[5]arene in the solid state.
Oxygenation of copper(I) with tetradentate tripodal ligands (L) comprised of a tris(aminoethyl)amine (tren) skeleton having sterically bulky substituent(s) on the terminal nitrogens has been investigated, whereAll the copper(I) complexes reacted with dioxygen at low temperatures to produce superoxocopper(II) and/ or trans-("-1,2-peroxo)-dicopper(II) complexes depending on the steric bulkiness of the terminal nitrogens and the reaction conditions. The reaction of a copper( þ ($0:24 mM) and higher dioxygen concentration (P(O 2 ) = $1 atm), the superoxo species is predominantly formed, whereas at a higher concentration of [Cu(L Me,Bn )] þ ($1 mM) and lower dioxygen concentration (P(O 2 ) = $0:02 atm) the formation of the peroxo species is observed.
(mu-Hydroxo or oxo)(mu-1,2-peroxo)diiron(III) complexes having a tetradentate tripodal ligand (L) containing a carboxylate sidearm [Fe2(mu-OH or mu-O)(mu-O2)(L)2]n+ were synthesized as models for peroxo-intermediates of non-heme diiron proteins and characterized by various physicochemical measurements including X-ray analysis, which provide fundamental structural and spectroscopic insights into the peroxodiiron(III) complexes.
We report a new route for the selective synthesis of di- and tetrafunctionalized pillararenes via oxidation and reduction of the pillararene units. Hypervalent-iodine oxidation of perethylated pillar[5]arene afforded pillar[5]arene derivatives containing one benzoquinone unit and two benzoquinones at the A,B- and A,C-units. A pillar[6]arene derivative containing one benzoquinone unit was also synthesized. Reduction of the benzoquinone units yielded position-selective di- and tetrahydroxylated pillararene derivatives. This methodology avoids the generation of many constitutional isomers and overcomes the isolation problem of numerous constitutional isomers. From these hydroxylated pillararenes, Huisgen reaction-based clickable di- and tetraalkynylated pillar[5]arenes were prepared. Because of the highly selective and reactive nature of Huisgen alkyne-azide cycloaddition, these pillar[5]arenes can serve as key compounds for a large library of di- and tetrafunctionalized pillararenes. Based on these di- and tetrafunctionalized pillar[5]arenes as key compounds, fluorescent sensors were created by the modification of di- and tetrapyrene moieties via Huisgen-type click reactions.
A new tetradentate tripodal ligand (L3) containing sterically bulky imidazolyl groups was synthesized, where L3 is tris(1-methyl-2-phenyl-4-imidazolylmethyl)amine. Reaction of a bis(mu-hydroxo)dicopper(II) complex, [Cu2(L3)2(OH)2]2+ (1), with H2O2 in acetonitrile at -40 degrees C generated a (mu-1,1-hydroperoxo)dicopper(II) complex [Cu2(L3)2(OOH)(OH)]2+ (2), which was characterized by various physicochemical measurements including X-ray crystallography. The crystal structure of 2 revealed that the complex cation has a Cu2(mu-1,1-OOH)(mu-OH) core and each copper has a square pyramidal structure having an N3O2 donor set with a weak ligation of a tertiary amine nitrogen in the apex. Consequently, one pendant arm of L3 in 2 is free from coordination, which produces a hydrophobic cavity around the Cu2(mu-1,1-OOH)(mu-OH) core. The hydrophobic cavity is preserved by hydrogen bondings between the hydroperoxide and the imidazole nitrogen of an uncoordinated pendant arm in one side and the hydroxide and the imidazole nitrogen of an uncoordinated pendant arm in the other side. The hydrophobic cavity significantly suppresses the H/D and 16O/18O exchange reactions in 2 compared to that in 1 and stabilizes the Cu2(mu-1,1-OOH)(mu-OH) core against decomposition. Decomposition of 2 in acetonitrile at 0 degrees C proceeded mainly via disproportionation of the hydroperoxo ligand and reduction of 2 to [Cu(L3)]+ by hydroperoxo ligand. In contrast, decomposition of a solid sample of 2 at 60 degrees C gave a complex having a hydroxylated ligand [Cu2(L3)(L3-OH)(OH)2]2+ (2-(L3-OH)) as a main product, where L3-OH is an oxidized ligand in which one of the methylene groups of the pendant arms is hydroxylated. ESI-TOF/MS measurement showed that complex 2-(L3-OH) is stable in acetonitrile at -40 degrees C, whereas warming 2-(L3-OH) at room temperature resulted in the N-dealkylation from L3-OH to give an N-dealkylated ligand, bis(1-methyl-2-phenyl-4-imidazolylmethyl)amine (L2) in approximately 80% yield based on 2, and 1-methyl-2-phenyl-4-formylimidazole (Phim-CHO). Isotope labeling experiments confirmed that the oxygen atom in both L3-OH and Phim-CHO come from OOH. This aliphatic hydroxylation performed by 2 is in marked contrast to the arene hydroxylation reported for some (mu-1,1-hydroperoxo)dicopper(II) complexes with a xylyl linker.
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