Synthesis and metal complexes of macrocyclic triamines bearing a phenol pendant

Kimura, Eiichi; Yamaoka, Masanori; Morioka, Mieko; Koike, Takao

doi:10.1021/ic00242a011

Cited by 32 publications

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“…1.462 (4) 1.460 (8) 1.480 (10) C( 12)-C(13) 1.527 (5) 1.515 (10) 1.526 (14) C(13)-C( 14) 1.523 (5) 1.513 (8) 1.515 (11) C(15)-C(16) 1.403 (4) 1.426 (7) 1.387 (9) C(15)-C(20)…”

Section: P2jaunclassified

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New-dimensional cyclam. Synthesis, crystal structure, and chemical properties of macrocyclic tetraamines bearing a phenol pendant

Kimura¹,

Koike²,

Uenishi³

et al. 1987

Inorg. Chem.

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Newly devised 13-15-membered macrocyclic tetraamine (N4) ligands attached with a phenolic pendant (10,11,13, and 15) have been synthesized to determine the influence of the phenol on the cation-enclosure properties of the macrocyclic N4 and, conversely, the influence of the proximate cations encompassed in N4 macrocycles on the chemical behavior of the phenolate pendant. The synthesis involves a novel annelation reaction between coumarin and suitable tetraamines. The favorable location of phenol in the periphery of the macrocycle has been confirmed by the X-ray crystal structure of the phenol-pendant 14-membered N4 (cyclam) lib. Dissociation of the phenolic protons is facilitated by incorporation of metal ions into the macrocycle, and the resulting phenolate ion atop stabilizes otherwise unstable complexes. The crystal structures of lib and its Cu11 complex 17a have been determined. The crystals of lib (C16H28N40) are monoclinic, space group P2¡/a, with four molecules in the unit cell of dimensions a = 15.335 (8) A, b = 8.535 (5) A, c = 13.331 (7) A, and ß = 105.17 (5)°. Crystals of 17a(C104)-H20 (C16H27N40CuC104-H20) are also monoclinic, space group P2¡/n, with four molecules in the unit cell of dimensions a = 30.943 (20) A, b = 8.188 (4) A, c = 7.936 (4) A, and ß = 95.89 (5)°. The structures were solved by the direct method for lib and the heavy-atom method for 17a and refined by block-diagonal least-squares calculations: for lib, R = 0.061 for 2635 independent reflections, and for 17a, R = 0.066 for 3703 independent reflections. The five-coordinate, square-pyramidal geometry around copper is illustrated with the phenolate oxygen at nearly the apex of the pyramid. The pH-metric and polarographic titration of Cun-llb revealed a complexation constant ([CuH_1L+]/[CuII][H_lL~]) of 1.0 X 1032 M"1 (H_,L is the phenolate species) and stability enhancement of ~10* 12 by the phenolate coordination. Its strong a donation contributes to stabilization of higher oxidation states of metal ions. Saturated polyamine macrocycles possess cavities capable of providing a favorable environment for the reception of guest cation and anion species.1 The strength of the ion binding is determined

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“…1.462 (4) 1.460 (8) 1.480 (10) C( 12)-C(13) 1.527 (5) 1.515 (10) 1.526 (14) C(13)-C( 14) 1.523 (5) 1.513 (8) 1.515 (11) C(15)-C(16) 1.403 (4) 1.426 (7) 1.387 (9) C(15)-C(20)…”

Section: P2jaunclassified

“…The oily residue was dissolved in dichloromethane and the solution washed with water, dried, and evaporated in vacuo. Addition of diethyl ether afforded 1,4,8,1 l-tetrakis(trifluoroacetyl)-5-(2-hydroxyphenyl)- 1,4,8,11 -tetraazacyclotetradecane (14) in 94% yield (1.14 g, 1.7 mmol): mp 184-187 °C. IR (KBr): vc0 = 1685 cm'1.…”

Section: P2jamentioning

confidence: 99%

New-dimensional cyclam. Synthesis, crystal structure, and chemical properties of macrocyclic tetraamines bearing a phenol pendant

Kimura¹,

Koike²,

Uenishi³

et al. 1987

Inorg. Chem.

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“…9 Indeed, phenolates have been successfully used by Kimura et al on other macrocyclic skeletons such as cyclam (1,4,8,11tetraazacyclotetradecane) and 1,5,9-triazacyclododecane in the form of a substituent of the macrocyclic framework. [10][11][12][13][14][15] On the other hand, Moore et al 16,17 and Wieghardt et al 18,19 used methylphenolic arms N-appended on tacn (1,4,7-triazacyclononane) to study complexes of trivalent metal ions such as gallium(III) and iron(III).…”

Section: Introductionmentioning

confidence: 99%

Cyclen derivatives with two trans-methylnitrophenolic pendant arms: a structural study of their copper(ii) and zinc(ii) complexes

et al. 2013

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Two new cyclen derivatives, H(2)do2nph and H(2)cb-do2nph, containing two trans-2-methyl-4-nitrophenol pendant arms and the latter including also an ethylene cross-bridge, were prepared in good yields using the bisaminal synthetic route. The two ligands were studied comparatively regarding their metal complexation behaviour. The copper(II) and zinc(II) complexes of H(2)do2nph and H(2)cb-do2nph were studied in dimethylsulfoxide-water (9 : 1 v/v) solution by a range of spectroscopic techniques. Copper(II) complexes were also studied in solid state by X-ray single crystal diffraction. These studies showed that the copper(II) and zinc(II) complexes of H(2)do2nph exhibited a distorted square pyramidal coordination environment with the four nitrogen atoms of the cyclen ring defining the basal plane, and that one of the nitrophenolate arms did not coordinate to the metal, independently of its protonation state. On the other hand, depending on the protonation state of one of the nitrophenolic arms, the cross-bridged derivative forms copper(II) complexes with distorted square pyramidal or octahedral geometries with one or two arms coordinated to the metal centre, respectively. In the complex with distorted octahedral geometry, the two phenolic oxygen atoms are coordinated to the metal centre in a cis-fashion. Acid-assisted dissociation assays in 1 mol dm(-3) HCl DMSO-H(2)O (9 : 1 v/v) solution at 298.2 K allowed one to determine the half-life of both copper(II) complexes, which is lower for the derivative without a cross-bridge as expected, while for the other one it is quite high and in line with similar cross-bridged cyclen derivatives from the literature.

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“…This method was applied to synthesis of a 13-membered tetraamine 40 31) and a 12-membered triamine 41. 32) In a similar fashion, a catechol-(42), 33) hydroquinone-(43), 30b) pyridyl-(44), 34,35) and imidazole-pendant cyclam derivatives (45) 36,37) were synthesized from each correspondingly substituted a,bunsaturated carboxyesters.…”

Section: ■■ 4 Ni II Complexes Of Cyclam Appended With a Ru Ii -Tris-mentioning

confidence: 99%

“…Biochemical Identification of the Zn-Cyclen Binding Sites in Natural DNAIn order to identify the interaction sites of Zn-cyclen complexes in natural DNA, a biochemical assay was employed with a DNA footprinting technique 81). Very useful information was obtained about the sequence-selective binding on 5ʼ-32 P-labeled DNA fragments (arbitrary 150 base pairs) from plasmid pUC19 by means of a combination of DNase I and micrococcal nuclease footprinting methods. For references, typical AT binders(distamycin A and DAPI )and a GC binder (echinomycin) were tested side by side on the same gel plate.…”

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confidence: 99%

Synthesis and metal complexes of macrocyclic triamines bearing a phenol pendant

Cited by 32 publications

References 0 publications

New-dimensional cyclam. Synthesis, crystal structure, and chemical properties of macrocyclic tetraamines bearing a phenol pendant

New-dimensional cyclam. Synthesis, crystal structure, and chemical properties of macrocyclic tetraamines bearing a phenol pendant

Cyclen derivatives with two trans-methylnitrophenolic pendant arms: a structural study of their copper(ii) and zinc(ii) complexes

Evolution of Macrocyclic Polyamines From Molecular Science to Supramolecular Science

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