Crystal structure and electronic properties of ammine[tris(2-aminoethyl)amine]copper(II) diperchlorate and potassium penta-amminecopper(II) tris(hexafluorophosphate)

Duggan, Mary; Ray, Noel J.; Hathaway, B. J.; Tomlinson, Gustav; Brint, Paul; Pelin, Kevin

doi:10.1039/dt9800001342

Cited by 206 publications

(148 citation statements)

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“…In all cases, the d-d transitions were at a higher energy than those reported for Cu(II) complexes based on classical tren ligands (Ϸ880 nm) (38,46), which is a reflection (54,55) (Fig. 9, which is published as supporting information on the PNAS web site) yielded straight lines with a slope n ϭ 1, confirming the formation of adducts with a 1:1 stoichiometry.…”

Section: Synthesis and Spectroscopic Characterization Of The Calix[6]mentioning

confidence: 63%

“…3, shows a copper center coordinated to the four nitrogen atoms of the calix [6]tren ligand and to one molecule of EtOH buried inside the calixarene cavity. The geometry at the metal center is trigonal bipyramidal (TBP) with a distorsion ( ϭ 0.70) (37) slightly more pronounced than those reported for other trenbased Cu(II) complexes (38)(39)(40)(41)(42)(43). For these classical systems, the angles between the axial ligands are always very close to 180°, whereas, in the calixarene system, the distortion of the TBP stems mainly from the low value of this angle (168.8°).…”

Section: Synthesis and Spectroscopic Characterization Of The Calix[6]mentioning

confidence: 87%

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Calix[6]tren and copper(II): A third generation of funnel complexes on the way to redox calix-zymes

Izzet

Douziech

Prangé

et al. 2005

Proc. Natl. Acad. Sci. U.S.A.

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Mono-copper enzymes play an important role in biology and their functionality is based on Cu(II)͞Cu(I) redox processes. Modeling a mono-nuclear site remains a challenge for a better understanding of its intrinsic reactivity. The first member of a third generation of calixarene-based mono-copper ''funnel'' complexes is described. The ligand is a calix[6]arene capped by a tren unit, hence presenting a N4 coordination site confined in a cavity. Its Cu(II) complexes were characterized by electronic and EPR spectroscopies. The x-ray structure of one of them shows a five-coordinated metal ion in a slightly distorted trigonal bipyramidal geometry thanks to its coordination to a guest ligand L (ethanol). The latter sits in the heart of the hydrophobic calixarene cone that mimics the active site chamber and the hydrophobic access channel of enzymes. bioinorganic ͉ supramolecular ͉ electrochemistry ͉ host-guest ͉ enzyme model C opper enzymes such as dopamine ␤-monooxygenase, peptidylglycine ␣-hydroxylating monooxygenase, and nitrate reductase present a mononuclear copper ion buried in their active pocket opened to the external medium through a selective substrate access channel. This organization is responsible for the efficiency and selectivity of their catalytic activity (1-6). A good chemical model for metalloenzymes is a key to the understanding of the fundamental mechanisms involved in the catalytic cycle and to the design of efficient and selective new tools for the synthetic chemist. Most classical models, however, irreversibly lead to dinuclear species because of the propensity of reactive cupric species to undergo dimerization (7-10). Trying to gain insights into the chemical and redox specificity (11-15) resulting from the proteic environment of mono-copper sites, we have developed a supramolecular system that mimics not only the polyhistidine binding core but also the hydrophobic pocket that controls the second coordination sphere of the metal and its binding to an exogenous molecule. The model is based on a calix[6]arene functionalized with a nitrogenous coordination core (16 -24). The first generation of such ligands (calix[6]N 3 , see Fig. 1) (16, 17) presents three amino arms that, upon binding to the copper ion, constrain the calix[6]arene into the cone conformation required to play the role of a host for a guest ligand L. The so-called funnel complexes best stabilize Cu(I) in a tetrahedral N 3 L environment (16, 18 -20), whereas the Cu(II) species adopt a square-based pyramidal geometry N 3 L(S) with the binding of a water molecule (S is H 2 O) as a fifth ligand that is added to the system by an upper access from the outside (21,22). Despite the coordination number change between both redox states, the calixarene cavity acts as a selective funnel for small neutral organic molecules (L) as a result of the innercavity coordination site. Interestingly, the guest ligand L was shown to play the role of a shoetree molecule (23, 24) that shapes the calixarene structure and fixes the global organization of the co...

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Section: Synthesis and Spectroscopic Characterization Of The Calix[6]mentioning

confidence: 63%

Section: Synthesis and Spectroscopic Characterization Of The Calix[6]mentioning

confidence: 87%

Calix[6]tren and copper(II): A third generation of funnel complexes on the way to redox calix-zymes

Izzet

Douziech

Prangé

et al. 2005

Proc. Natl. Acad. Sci. U.S.A.

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“…The magnetically-dilute polycrystalline complex (2) exhibits a reversed electron paramagnetic resonance (EPR) spectrum expected for a Cu" dopant having approximately trigonal-bipyramidal coordination geometry (Duggan, Ray, Hathaway, Tomlinson, Brint & Pelin, 1980). Simulation studies using the program QPOWA (Belford, 1987) show these spectra are consistent with a single Cu" dopant site having the parameters g± = 2.145, A.…”

mentioning

confidence: 64%

Isostructural trigonal-bipyramidal CuII and nominally 1% CuII-doped ZnII complexes with N5 ligation

Stibrany¹,

Potenza²,

Schugar³

1993

Acta Crystallogr C

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“…[20][21][22][23] It has been widely observed that regular and distorted trigonal bipyramidal copper(II) complexes exhibit an absorption band at > 670 nm, whereas square-pyramidal copper(II) complexes show an absorption band at considerably shorter wavelength. [20][21][22] Therefore, the coordination geometry may be considered intermediate between TBP and SP in the solid state. Unfortunately, we Notes were unable to isolate single crystals of the complex suitable for X-ray work.…”

Section: Resultsmentioning

confidence: 99%

Synthesis and Characterization of New Tetraaza Macrocycles Bearing Two or Four N-Methoxyethyl Pendant Arms and Their Copper(II) and/or Nickel(II) Complexes

Kang¹,

Kim²,

Kwak³

2010

Bulletin of the Korean Chemical Society

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Crystal structure and electronic properties of ammine[tris(2-aminoethyl)amine]copper(II) diperchlorate and potassium penta-amminecopper(II) tris(hexafluorophosphate)

Abstract: Crystal Structure and Electronic Properties of Ammine[tris(2-aminoethyl)amine]copper(i~) Diperchlorate and Potassium Penta-amminecopper( 11) Tris( hexaf luorophosphate)By M a r y Duggan, Noel Ray, Brian Hathaway,' and (in part)

Cited by 206 publications

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Calix[6]tren and copper(II): A third generation of funnel complexes on the way to redox calix-zymes

Calix[6]tren and copper(II): A third generation of funnel complexes on the way to redox calix-zymes

Isostructural trigonal-bipyramidal CuII and nominally 1% CuII-doped ZnII complexes with N5 ligation

Synthesis and Characterization of New Tetraaza Macrocycles Bearing Two or Four N-Methoxyethyl Pendant Arms and Their Copper(II) and/or Nickel(II) Complexes

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