Aqua complexes of 18—crown-6 with H3PO4, H2TiF6, and HNO3: synthesis and vibrational spectra

Chênevert, Robert; Rodrigue, André; Chamberland, Daniel; Ouellet, Jacques; Savoie, Rodrigue

doi:10.1016/0022-2860(85)87020-4

Cited by 12 publications

(8 citation statements)

References 25 publications

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“…Izatt et al 22 showed that stable crystalline complexes between the hydronium ion and cis-syn-cis-cyclohexano-18-crown-6 can be prepared. Further work by Weber et al, 23 Chevenert et al, 24,25 Junk and Atwood, 26 McKenna and Eyring, 27 and Koltoff and Chantooni 28 have also reported the formation, isolation and spectroscopic identification of similar complexes. Leis et al 29 have described the complexation of hydronium ions at the surfaces of hydrogen dodecyl sulfate micelles.…”

Section: ■ Results and Discussionmentioning

confidence: 90%

Involvement of Supramolecular Complexes in the Capture and Release of Protonic Acids During the Cationic Ring-Opening Polymerization of Epoxides

2012

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The kinetics of the cationic ring-opening polymerizations of epoxide monomers were controlled through the use of supramolecular proton complexes. α,ω-Diglycidyl oligoethylene oxides bearing multiple ethyleneoxy spacer groups form metastable supramolecular proton complexes with strong Brønsted acids generated either by the photolysis of onium salts or by their redox reactions with reducing agents. Trapping of the Brønsted acids by in situ complex formation results in a delay of the onset of cationic ring-opening. However, once polymerization begins, the epoxide groups of the monomer are very rapidly consumed resulting in characteristically highly exothermic autoaccelerated polymerization reactions. Crown ethers can also form supramolecular complexes with hydronium ions derived from the reaction of protonic acids with water and these complexes can be used to modify the kinetic behavior of the cationic ring-opening thermal and photopolymerizations of a variety of epoxide monomers. The ring size of a crown ether has a strong influence on the stability of the supramolecular complex formed, and this was shown to have a major impact on the kinetics of the cationic ring-opening polymerizations.

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Section: ■ Results and Discussionmentioning

confidence: 90%

Involvement of Supramolecular Complexes in the Capture and Release of Protonic Acids During the Cationic Ring-Opening Polymerization of Epoxides

2012

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“…Recent examples of the use of macrocycles to stabilize six-27 and eight-coordinate magnesium28 have appeared, but to our knowledge this is the third example of a seven-coordinate magnesium atom. 25,29…”

Section: Resultsmentioning

confidence: 99%

Synthesis of salts of the hydrogen dichloride anion in aromatic solvents. 2. Syntheses and crystal structures of [K.cntdot.18-crown-6][Cl-H-Cl], [Mg.cntdot.18-crown-6][Cl-H-Cl]2, [H3O.cntdot.18-crown-6][Cl-H-Cl], and the related [H3O.cntdot.18-crown-6][Br-H-Br]

Atwood¹,

Bott²,

Means³

et al. 1990

Inorg. Chem.

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the structure was straightforward from application of the heavy-atom method. Space group Pbca was confirmed and the position of the iron atom was deduced from the three-dimensional Patterson function. The positions of the remaining non-hydrogen atoms were determined through subsequent Fourier and difference Fourier calculations.Least-squares refinementz9 of the 35 non-hydrogen atoms, varying the iron atom anisotropically, produced unweighted and weighted residuals of 8.7% and 7.1%,'O respectively. Hydrogen atom positions were calcu-lated by using a C-H distance of 0.95 8, and an isotropic thermal parameter of 6.0 Az. Further refinement resulted in residuals of R = 7.2% and R, = 5.5%. The final difference Fourier map had no peak greater than 0.26 e/8,'.Acknowledgment is made to the National Institutes of Health (GM 28938) and the Department of Energy, Office of Basic Energy Sciences (85ER 13430), for support of this work. Tables of complete anisotropic and isotropic temperature factors, bond distances and angles, calculated hydrogen positions, and defined planes and calculated dihedral angles for 2 (3 pages); a table of calculated and observed structure factors for 2 (IO pages). Ordering information is given on any current masthead page. The reaction of HCI(g), H 2 0 , and 18-crown-6 in toluene gives [H30.18-crown-6] [CI-H-C1]-3.6tol (to1 = toluene), from which crystals of [H30.18-crown-6] [CI-H-CIJ are isolated: space group P2,/c; a = 10.475 (7), b = 20.767 (9), c = 8.583 (7) 8,; @ = 96.23 (3)'; Z = 4 for D, = 1.28 g cW3; R = 0.042 for 493 independent observed reflections. The liquid clathrate [H30.18crown-61 [CI-H-CI].3.6tol dissolves KCI, and upon standin , the solution affords crystals of [K.18-crown-6] [CI-H-CI]: space group P2,/c; a = 8.325 (2), b = 14.094 (4), c = 7.893 (6) ! ; @ = 98.56 (4)'; 2 = 2 for 0, = 1.37 g cm-'; R = 0.055 for 1194 independent observed reflections. In a similar fashion, the liquid clathrate dissolves MgCI, and yields [Mg18-crown-6] [C1-H-Cll2: space group Pbca; a = 18.310 (7), b = 7.512 (6), c = 29.085 ( 8 ) A; Z = 8 for D, = 1.44 g cm-'; R = 0.066 for 1204 observed reflections. The [Br-H-BrI-anion is produced by the reaction of HBr(g), HzO, and 18-crown-6 in toluene. [H30.18-crown-6][Br-H-Br] is isomorphous with the [CI-H-CI]-analogue, and the crystals belong to space group P2,/c with a = 10.588 ( I ) A, b = 21.060 (2) A, c = 8.753 ( I ) A, @ = 95.25 (4)O, and D, = 1.52 g cm-' for Z = 4; R = 0.059 for 1697 observed reflections. Supplementary Material Available:The CI-.CI separations range from 3.11 ( I ) 8, in the H30+ salt to 3.331 (2) 8, in the Mg2+ analogue. The angle at the hydrogen atom in the hydrogen dichloride ranges from 161' for the [Mg18-cro~n-6]~+salt to 180° for the [K.18-crown-6]+salt. The short CI-CI separations in the H30+ and K+ salts are attributed to the absence of a strong directional interaction of the anion with the cation. For the long CI-.CI in the Mgz+ case, the magnesium atom is bonded to one of the chlorine atoms at 2.428 (6) and 2.454 (3) A (two indepen...

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“…The distances of 2.3260(7) and 2.6677 (9) A for the Pd-Cl bridge and Pd-Cl term are normal (24,25). The bond angles around the metal centers, 85.89(3)-92.47(3)", reflect the fact that the geometry is distorted from the planar shape due to the close arrangement of the Pd atoms.…”

Section: The Hexachlorodipalladate(ll) Anionmentioning

confidence: 99%

“…With weak acids (pK, of the acid > pK, of H30+ at -1.7) such as carboxylic acids and weak inorganic acids, neutral component complexes have been obtained (8,9). These usually have a 1: 1: 1 or 2:2: 1 (acid:water:crown) stoichiometry, although some anhydrous complexes have been reported (8,10).…”

Section: Introductionmentioning

confidence: 99%

Complexes of 18-crown-6 with oxonium ions derived from transition metal chlorides and hydrochloric acid: 18-crown-6.H₃O⁺. FeCl₄⁻, 18-crown-6.H₃O⁺.InCl₄⁻, (18-crown-6.H₃O⁺)₂.Pd₂Cl₆²⁻

Chênevert¹,

Chamberland²,

Simard³

et al. 1989

Can. J. Chem.

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Can. J. Chem. 67, 32 (1989). The macrocyclic polyether 18-crown-6 forms complexes with hydrates of strong acids derived from transition metal chlorides and hydrochloric acid. The following charged-component complexes have been isolated and characterized:18-crown-6. H 3 0 + . FeC14-, 18-crown-6. H30+ . InC14-, and (18-crown-6. H30+)2. pd2Cls2-. X-ray diffraction study of the palladium complex is reported. The oxonium ion is located at the center of the macrocyclic ether cavity and the symmetry of the ring is close to D3d.

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Aqua complexes of 18—crown-6 with H3PO4, H2TiF6, and HNO3: synthesis and vibrational spectra

Cited by 12 publications

References 25 publications

Involvement of Supramolecular Complexes in the Capture and Release of Protonic Acids During the Cationic Ring-Opening Polymerization of Epoxides

Involvement of Supramolecular Complexes in the Capture and Release of Protonic Acids During the Cationic Ring-Opening Polymerization of Epoxides

Synthesis of salts of the hydrogen dichloride anion in aromatic solvents. 2. Syntheses and crystal structures of [K.cntdot.18-crown-6][Cl-H-Cl], [Mg.cntdot.18-crown-6][Cl-H-Cl]2, [H3O.cntdot.18-crown-6][Cl-H-Cl], and the related [H3O.cntdot.18-crown-6][Br-H-Br]

Complexes of 18-crown-6 with oxonium ions derived from transition metal chlorides and hydrochloric acid: 18-crown-6.H₃O⁺. FeCl₄⁻, 18-crown-6.H₃O⁺.InCl₄⁻, (18-crown-6.H₃O⁺)₂.Pd₂Cl₆²⁻

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Aqua complexes of 18—crown-6 with H3PO4, H2TiF6, and HNO3: synthesis and vibrational spectra

Cited by 12 publications

References 25 publications

Involvement of Supramolecular Complexes in the Capture and Release of Protonic Acids During the Cationic Ring-Opening Polymerization of Epoxides

Involvement of Supramolecular Complexes in the Capture and Release of Protonic Acids During the Cationic Ring-Opening Polymerization of Epoxides

Synthesis of salts of the hydrogen dichloride anion in aromatic solvents. 2. Syntheses and crystal structures of [K.cntdot.18-crown-6][Cl-H-Cl], [Mg.cntdot.18-crown-6][Cl-H-Cl]2, [H3O.cntdot.18-crown-6][Cl-H-Cl], and the related [H3O.cntdot.18-crown-6][Br-H-Br]

Complexes of 18-crown-6 with oxonium ions derived from transition metal chlorides and hydrochloric acid: 18-crown-6.H3O+. FeCl4−, 18-crown-6.H3O+.InCl4−, (18-crown-6.H3O+)2.Pd2Cl62−

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Complexes of 18-crown-6 with oxonium ions derived from transition metal chlorides and hydrochloric acid: 18-crown-6.H₃O⁺. FeCl₄⁻, 18-crown-6.H₃O⁺.InCl₄⁻, (18-crown-6.H₃O⁺)₂.Pd₂Cl₆²⁻