Isolation of a spin-frustrated imidazolate-bridged trinuclear copper(<scp>II</scp>) complex potentially relevant to the multicopper oxidases

Chaudhuri, Phalguni; Karpenstein, Ina; Winter, Manuela; Butzlaff, Christian; Bill, Eckhard; Trautwein, Alfred X.; Flörke, Ülrich; Haupt, H.‐J.

doi:10.1039/c39920000321

Cited by 85 publications

(60 citation statements)

References 23 publications

Supporting

Mentioning

Contrasting

Unclassified

Order By: Relevance

“…The negative isotropic exchange coupling constant found for 1 (À115 cm À1 ) matches the data on similar tri-copper complexes: the triangulo-shaped (À75 cm À1 ) [11], the V-shaped (À61 cm À1 ) [29], and the linear one (À118 cm À1 ) [30]; the J-values are given in conformity with Eq. (3).…”

supporting

confidence: 70%

“…Only in the case of [Cu(can) 2 (imidazole) 2 ], it was detected that the cyanamidonitrate forms bridges through nitrile nitrogen and oxygen atoms [5]. Thus, cyanamidonitrate exhibits only a weak ability to form bridges between central atoms.The family of the imidazolato-containing Cu(II) complexes is nowadays rich and it embraces: (i) katena-imidazolato complexes [6,7], (ii) binuclear systems [8,9], (iii) trinuclear complexes [10,11], (iv) and tetranuclear system [12,13]. Some of these complexes were studied in connections with important biological functions.…”

mentioning

confidence: 99%

See 1 more Smart Citation

A trinuclear cyanamidonitrate–copper(II) complex bridged by imidazolato ligands

Boča

Hvastijová

Kožı́šek

et al. 2005

Inorganic Chemistry Communications

View full text Add to dashboard Cite

supporting

confidence: 70%

mentioning

confidence: 99%

A trinuclear cyanamidonitrate–copper(II) complex bridged by imidazolato ligands

Boča

Hvastijová

Kožı́šek

et al. 2005

Inorganic Chemistry Communications

View full text Add to dashboard Cite

“…A fourth N atom from the L ligand completes the coordination in the axial position with a distinctly longer Cu--N(1) bond length of 2.255 (10) A. This geometry has been observed previously in other square-pyramidal L complexes of copper(II) (Chaudhuri et al, 1991(Chaudhuri et al, , 1992. The N30 coordination plane around the copper and the plane of the oxamidato group form a dihedral angle of 8.6 °.…”

Section: Commentsupporting

confidence: 48%

Ring cleavage of imidazole to oxamide by reaction with dioxygen in the presence of a CuI–amine complex. Structure of μ-oxamidato-bis[(1,4,7-trimethyl-1,4,7-triazacyclononane)copper(II)] triiodide iodide

Flörke¹,

Haupt²,

Karpenstein³

et al. 1993

Acta Crystallogr C

View full text Add to dashboard Cite

An oxamidato group in a trans conformation bridges two trirnethyltriazacyclononane moieties. Each Cu atom is fivefold coordinated by four N and one O atoms. The N and O atoms of the oxamidato ligand are disordered over two sites giving two different trans conformations. The cations are packed along [ 100] with iodide and triiodide anions between them. The 13-ions are disordered and have asymmetric I--I bond lengths.

show abstract

“…field of supramolecular coordination chemistry [10] examples of molecular triangles with metal atoms in vertex positions are still relatively rare and have so far been concentrated on noble metals, [11±15] copper, [16] and ligands based on nitrogen-containing heterocycles. In contrast, the novel molecular triangle 1 consists of catecholate ligands in combination with cis-MoO 2 2 units, demonstrating the versatility of these components as building blocks in supramolecular assemblies.…”

mentioning

confidence: 99%

Stereoselectivity in the Formation of a Cyclic Trinuclearcis-Dioxomolybdenum(VI) Complex of a Chiral Siderophore Analogue

Duhme‐Klair¹,

Vollmer²,

Mars³

et al. 2000

Angew. Chem. Int. Ed.

View full text Add to dashboard Cite

The stereoselective synthesis of coordination compounds can be achieved by using enantiomerically pure ligands, which, on metal binding, transfer their chiral information to the metal center. [1] Siderophores, high-affinity chelators synthesized by microorganisms to solubilize iron(iii) for uptake into the cell, represent a biologically important example of this ligand type. [2] Most siderophores are enantiomerically pure amino acid derivatives, and the chirality of the molecules can play an important role in their biological activity. This is well documented for enterobactin, the native siderophore of Escherichia coli: Only the naturally occurring complex, having an l-seryl ligand backbone and a D configuration at the metal center, is able to supply iron to the cells. [3,4] Interestingly, the N 2 -fixing cells of Azotobacter vinelandii secrete azotochelin (Scheme 1), a tetradentate iron Scheme 1. siderophore which also binds molybdenum. [5, 6] The structures of relevant model complexes have been reported. [7,8] Molybdenum, as well as iron, is a component of the conventional nitrogenase, and in A. vinelandii the siderophore production depends not only on the amount of iron in the environment but also on the concentration of molybdenum. [5b, 6b] We report here that the l-lysine derivative azotochelin shows a high diastereoselectivity in forming the two possible D and L cisdioxomolybdenum complexes. Use of the azotochelin analogue H 4 -(1R,2R)-dachcam (Scheme 1) allowed us to investigate the chiral induction on molybdenum binding in the solid state and to compare the CD spectra of the model complex Further study of the magnetic properties of these irregular alternating systems are planned but a general law may be easily envisaged for homometallic systems with sequences of more than one F/AF interaction. Ferromagnetism emerges, as observed for 2, if 2n1 AF interactions are followed by one or more F interactions; the ground state here is always S 0. An alternative possibility consists of an even number of AF interactions (2n) followed by one or more (m) F interactions, as observed for 1, which induces net ferrimagnetic behavior with ground state S T m S for each (2nm) local S spin carrier. 3 ], Z 6 [10], 1 calc 1.451 g cm À3 [1.593 g cm À3 ], crystal size 0.15 Â 0.28 Â 0.50 mm [0.30 Â 0.60 Â 1.0 mm], m 0.893 mm À1 [0.807 mm À1 ]. Of 4887 [17 574] reflections collected, 3164 [6593] were observed with I > 2s(I); 289 [612] parameters. R(F) 0.0363 [0.0641], wR(F 2 ) 0.0943 [0.1861], min./max. residual electon density 1 À 0.22/0.21 e À3 [À 1.94/ 1.80 e À3 ]. The data were collected on a modified STOE [IPDS] diffractometer with Mo Ka irradiation 0.71069 [0.71073 ] at room temperature. Lorentz polarization effects, intensity decay, and absorption (DIFABS) [Lorentz polarization effects and numerical absorption (X-SHAPE, min./max. transmission 0.604/0.803)] corrections were made. Both structures were solved by direct methods and refined by full-matrix least-squares method on F 2 values. Refinement used the SHELXTL/PC packag...

show abstract

Isolation of a spin-frustrated imidazolate-bridged trinuclear copper(II) complex potentially relevant to the multicopper oxidases

Cited by 85 publications

References 23 publications

A trinuclear cyanamidonitrate–copper(II) complex bridged by imidazolato ligands

A trinuclear cyanamidonitrate–copper(II) complex bridged by imidazolato ligands

Ring cleavage of imidazole to oxamide by reaction with dioxygen in the presence of a CuI–amine complex. Structure of μ-oxamidato-bis[(1,4,7-trimethyl-1,4,7-triazacyclononane)copper(II)] triiodide iodide

Stereoselectivity in the Formation of a Cyclic Trinuclearcis-Dioxomolybdenum(VI) Complex of a Chiral Siderophore Analogue

Contact Info

Product

Resources

About