A tricopper(II) complex containing a triply bridging carbonate group

Kolks, Gary; Lippard, Stephen J.; Waszczak, J. V.

doi:10.1021/ja00534a045

Cited by 86 publications

(42 citation statements)

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“…The Cu-N distances of ca. 2 A, observed in I and 11, are typical of similar distances found in a variety of copper(I1) complexes (20)(21)(22)(23)(24). The distances and angles within the PAP ligands of both complexes are comparable, and are similar to those observed in both molecules of VII.…”

Section: Description Of the Structures Of Cotnpounds L A N D I1supporting

confidence: 72%

Copper tetrafluoroborate complexes of the potentially binucleating ligand 1,4-di(2′-pyridyl)aminophthalazine. Mononuclear and polynuclear derivatives

Dewan¹,

Thompson²

1982

Can. J. Chem.

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Three different copper tetrafluoroborate complexes are obtained from the reaction of copper tetrafluoroborate and the title ligand (PAP) in water. Two crystalline modifications of a six-coordinate mononuclear protonated derivative, [Cu(PAPH)2(H2O)2](BF4)4, a triclinic brown form (I) and a monoclinic green form (II), and a dark green polynuclear complex containing neutral ligand and formulated as [Cu3(PAP)2(OH)2](BF4)(BF3OH)3•5H2O (III), are obtained from the same reaction mixture. The hydrolysis of BF4− in water is thought to be responsible for the formation of protonated PAP. In methanol a four-coordinate protonated derivative, [Cu(PAPH)2](BF4)4 (IV) and a binuclear complex [Cu2(PAP)2(H2O)2](BF4)4•0.5MeOH (V), containing neutral ligand, are obtained. The molecular structures of both forms of [Cu(PAPH)2(H2O)2](BF4)4 have been determined by single crystal X-ray diffraction. The brown triclinic form (I) belongs to space group [Formula: see text] with a = 9.856(1), b = 12.724(1), c = 9.401(1) Å, α = 101.691(8), β = 96.717(9), γ = 70.145(8)°, V = 1084.4 Å3, Z = 1. The green monoclinic form (II) belongs to space group P21/n with a = 12.663(4), b = 9.573(3), c = 18.813(4) Å, β = 107.16(2)°, V = 2178.9 Å3, Z = 2. Both complexes have tetragonally distorted six-coordinate structures involving axially bound water molecules and two in plane bidentate protonated ligands. The major difference between the structures involves the axial Cu—O(W) bond lengths (triclinic 2.497(9) Å; monoclinic 2.426(9) Å).

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Section: Description Of the Structures Of Cotnpounds L A N D I1supporting

confidence: 72%

Copper tetrafluoroborate complexes of the potentially binucleating ligand 1,4-di(2′-pyridyl)aminophthalazine. Mononuclear and polynuclear derivatives

Dewan¹,

Thompson²

1982

Can. J. Chem.

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“…The weak axial interaction Cu-O3 is broken in 7 , which features carbonate bound to three Cu(II) ions in η 1 fashion, a precedented tricopper-carbonate motif. [15] Again, intramolecular hydrogen bonds between the macrocycle NH groups and the carbonate O atoms occurs, here resulting in complete sequestration of all of the available electron lone pairs of the carbonate ion in the complex.…”

Section: Resultsmentioning

confidence: 99%

Secondary Sphere Hydrogen Bonding in Monocopper Complexes of Potentially Dinucleating Bis(carboxamide) Ligands

et al. 2015

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Reaction of a macrocyclic ligand precursor comprising two bis(carboxamido)pyridine units (H4L4) connected by ethylene linkers with NMe4OH and CuX2 (X = Cl, OAc, or OTf) yielded monocopper complexes [NMe4][(H2L4)Cu(X)] (X = Cl (3), OAc (4), or OH (5)), in contrast to previous work using a related ligand with ortho-phenylene linkers wherein dicopper compounds were isolated. X-ray structures of the complexes revealed hydrogen bonding from the free carboxamide N-H groups in the doubly protonated form of the ligand (H2L4−) to the monodentate fourth ligand coordinated to the Cu(II) ion. Similar secondary sphere hydrogen bonding interactions were identified in multinuclear compounds [NMe4]2[((H2L4)Cu)n(CO3)] (n = 2 or 3) that were isolated from exposure of 5 to air. Cyclic voltammetry revealed oxidations of 3 and 5 at potentials ~300 mV higher than analogous monocopper complexes of bis(arylcarboxamido)pyridine ligands which lack the intramolecular hydrogen bonds, consistent with removal of electron density from the metal center by the hydrogen bonding array. Another ligand variant (H4L5) with ortho-phenylene linkers and only one bis(carboxamido)pyridine moiety yielded monocopper complexes [NMe4][(H2L5)Cu(OAc)] • DMF (8) and [NMe4][(H2L5)CuCl)] • CH3CN (9), but the X-ray structures revealed a different hydrogen bonding arrangement to the solvate molecules. Nonetheless, a high redox potential for 9 was observed, consistent with intramolecular hydrogen bonding interactions in solution.

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“…The Cu II ions are weakly coupled in a ferromagnetic manner, as also observed 4 , and is J ϭ 8.94, zJЈ ϭ Ϫ0.075 cm Ϫ1 (ref. [5] ). Ϫ [d] No intercluster interaction was considered in the fitting procedure.…”

Section: Resultsmentioning

confidence: 99%

A Novel Triangular Trinuclear μ3-CO3 Ferromagnetic CuII Compound Prepared in situ from CO2 Uptake in Air. X-ray Structure, Spectroscopy and Magnetism

Albada

Mutikainen

Roubeau

et al. 2000

Eur. J. Inorg. Chem.

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The new trinuclear compound [Cu3(bpy)6(μ3‐CO3)](BF4)4(H2O)2(C2H6O) (in which bpy = 2,2′‐bipyridine) has been synthesized from Cu(BF4)2 and bpy in aqueous ethanol by rapid uptake of atmospheric CO2. The structure of the compound has been determined by X‐ray crystallography; it was found to crystallise in the triclinic space group P1¯ with a = 13.405(7), b = 13.691(7), c = 21.446(8) Å, α = 82.87(4), β = 73.57(4), γ = 64.32(4)°, Z = 2. The three copper atoms are connected to each other through the oxygen atoms from the bridging carbonato group, giving a triangular array of copper atoms. Each copper has a distorted square‐pyramidal environment with a basal plane formed by three nitrogen atoms of the two chelating bipyridine groups and the oxygen atom of the bridging carbonato group (Cu−N/O distances about 2.0 Å). The apical position is formed at each copper by the fourth nitrogen atom of the bipyridines with distances varying from 2.120(5) to 2.188(5) Å. A weak ferromagnetic interaction is observed between the copper(II) ions. All data were fitted using the Hamiltonian H = −J12 (S1·S2) −J13 (S1·S3) −J23 (S2·S3). Observed parameters are J = 10.6 cm−1 and a very weak antiferromagnetic intercluster interaction with zj′ = −1.2 cm−1.

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A tricopper(II) complex containing a triply bridging carbonate group

Cited by 86 publications

References 0 publications

Copper tetrafluoroborate complexes of the potentially binucleating ligand 1,4-di(2′-pyridyl)aminophthalazine. Mononuclear and polynuclear derivatives

Copper tetrafluoroborate complexes of the potentially binucleating ligand 1,4-di(2′-pyridyl)aminophthalazine. Mononuclear and polynuclear derivatives

Secondary Sphere Hydrogen Bonding in Monocopper Complexes of Potentially Dinucleating Bis(carboxamide) Ligands

A Novel Triangular Trinuclear μ3-CO3 Ferromagnetic CuII Compound Prepared in situ from CO2 Uptake in Air. X-ray Structure, Spectroscopy and Magnetism

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