Copper complexes of 2,6-bis(iminomethyl)pyridine derivatives and of 1,3-bis(pyridin-2-yl)pyrazole. Effects of ligand bulk and conformational strain on the ground state of a six-co-ordinate copper(II) ion

Holland, Joanne M.; Liu, Xiaoming; Zhao, Jing; Mabbs, Frank E.; Kilner, Colin A.; Halcrow, Malcolm A.

doi:10.1039/b005105p

Cited by 49 publications

(53 citation statements)

References 38 publications

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“…It must be stressed that the present analysis does not tell us whether those structures correspond to genuine inverted Jahn-Teller distortions or not. Interestingly, among three compounds in which tridentate ligands impose an unambiguous compressed tetragonal bipyramid, [52,53] the 1 value is clearly discriminating in two cases (34.7 and 34.5), [52] but inconclusive in the other (32.6), [53] because severe bond-angle distortions place that compound away from the pure tetragonal compression path.…”

Section: From Tetrahedral To Trans Octahedralmentioning

confidence: 93%

Ligand Association/Dissociation Paths and Ill‐Defined Coordination Numbers

Ruiz‐Martínez

Casanova

Álvarez

2010

Chemistry A European J

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The continuous shape measures approach provides a means for handling the common situation in which a metal atom presents an ill-defined coordination number. Those cases are characterized by the presence of secondary interactions to Lewis bases at distances significantly longer than those expected for a chemical bond. Systematic ways of analyzing ligand association/dissociation pathways that describe such structures and their application to a variety of specific cases are presented. The concepts and methodology presented here apply to molecules and extended solids as well and provide, when needed, a more flexible and precise stereochemical description of the metal coordination sphere than that of an integer coordination number and the associated polyhedral shape.

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Section: From Tetrahedral To Trans Octahedralmentioning

confidence: 93%

Ligand Association/Dissociation Paths and Ill‐Defined Coordination Numbers

Ruiz‐Martínez

Casanova

Álvarez

2010

Chemistry A European J

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“…These bond distances, particularly for the intermediate bonds Cu1-N9 and Cu1-N12, are characteristic of a compound of this type with a {d z 2 } 1 configuration (structure B, Fig. 1; Holland et al, 2000;Solanki et al, 1998Solanki et al, , 2001). The hydroxyl groups of ligand N2-O13 each donate a hydrogen bond to a different acetone molecule, while those of the other ligand N14-O25 form hydrogen bonds to the two perchlorate ions (Fig.…”

Section: Figurementioning

confidence: 99%

“…Ten years ago, we first reported that the electronic structure of D 2d -symmetric copper(II) complexes of meridional tridentate imine ligands can be controlled, by steric or conformational effects (Solanki et al, 1998(Solanki et al, , 2001Bridgeman et al, 1999;Holland et al, 2000). Thus, for example, homoleptic copper(II) complexes of 2,6-bis(iminomethyl)pyridine derivatives (L R , Fig.…”

Section: Introductionmentioning

confidence: 99%

“…Thus, for example, homoleptic copper(II) complexes of 2,6-bis(iminomethyl)pyridine derivatives (L R , Fig. 1) can adopt two different electronic structures, depending on the identity of the 'R' substituents (Holland et al, 2000;Salaudeen et al, 2008). Smaller substituents like methyl, cyclohexyl or a benzyl derivative give complexes with the usual pseudo-Jahn-Teller elongated structure by crystallography and/or EPR, which in this case corresponds to a lengthening of two of the distal Cu-N{aldimine} bonds (structure A, Fig.…”

Section: Introductionmentioning

confidence: 99%

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Change in electronic structure in a six-coordinate copper(II) complex accompanied by an anion order/disorder transition

Kilner

Halcrow

2010

Acta Crystallogr Sect B

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A variable-temperature crystallographic study of [Cu(L(OH))(2)][ClO(4)](2).2(CH(3))(2)CO [L(OH) = 2,6-bis(hydroxyiminomethyl)pyridine] between 30 and 300 K is presented. The complex exhibits an unusual electronic structure at room temperature with a {d(z(2))}(1) ground state, corresponding to an axially compressed ligand coordination geometry about the copper ion. This reflects a suppression of the pseudo-Jahn-Teller distortion that is normally shown by copper(II) compounds with this ligand geometry [Halcrow et al. (2004). New J. Chem. 28, 228-233]. On cooling the compound undergoes an abrupt structural change at 157 +/- 3 K, that does not involve a change in the space group (P1), but causes significant changes to c and the unit-cell angles. This reflects a conformational rearrangement of the complex dication, towards a more typical pseudo-Jahn-Teller elongated coordination geometry. This occurs concurrently with a crystallographic ordering of one of the two perchlorate anions, and a significant displacement of the two lattice acetone molecules. The transformation involves displacements of up to 0.5 A in the non-H atoms of the structure at 30 K, compared with their positions at 300 K. The change in coordination geometry of the complex around 157 K is reflected in a small reduction in its magnetic moment near that temperature.

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“…En complejos de CuN 6 , con dos nitrógenos piridínicos trans, y cuatro nitrógenos de imina, la banda a 709nm es atribuida a bandas d-d (83) . (ε=43 dm 3 mol -1 cm -1 ) con Cu(II) en coordinación pseudoctaédrica (84).…”

Section: Especieunclassified

Estudio de especiación química de los fármacos antiinflamatorios tenoxicam y piroxicam con cationes metálicos de interés biológico

Hernández

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Copper complexes of 2,6-bis(iminomethyl)pyridine derivatives and of 1,3-bis(pyridin-2-yl)pyrazole. Effects of ligand bulk and conformational strain on the ground state of a six-co-ordinate copper(II) ion

Cited by 49 publications

References 38 publications

Ligand Association/Dissociation Paths and Ill‐Defined Coordination Numbers

Ligand Association/Dissociation Paths and Ill‐Defined Coordination Numbers

Change in electronic structure in a six-coordinate copper(II) complex accompanied by an anion order/disorder transition

Estudio de especiación química de los fármacos antiinflamatorios tenoxicam y piroxicam con cationes metálicos de interés biológico

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