On the Coordination Number of the Metal in Crystalline Halogenocuprates(I) and Halogenoargentates(I)

Jagner, Susan; Helgesson, Göran

doi:10.1016/s0898-8838(08)60004-5

Cited by 103 publications

(79 citation statements)

References 149 publications

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“…The ion acceleration energy pulse length and collision time were varied to obtain the minimum energy to effect dissociation in one collision. The centre of mass translational kinetic energy E com of an activated ion was calculated using Equation (1), where m t is the mass of the argon target, m p…”

Section: Mass Spectrometric Methodsmentioning

confidence: 99%

Supramolecular Assemblies of Quaternary Ammonium Cations and Halide Anions in the Gas Phase: ESMS-FTICR Data and Computer Modelling

Hasselgren¹,

Fisher²,

Jagner³

et al. 2000

Chem. Eur. J.

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Supramolecular aggregates of tetraalkylammonium halides (R4NX) are formed by electrospray out of acetonitrile solution. Mass spectrometry reveals 88 charged aggregates for R= Me, Et, Bu; X= Br, I, ranging up to [(Bu4N)39Br42]3- in size. With the objective of improving calculations of intermolecular energies for supramolecular aggregates of ions, calibrated semi-empirical potentials for inter-ion interactions have been developed and applied to these aggregates. The accuracy of the calculated energies is supported by the measured collisional dissociation energy of (Et4N+)4 (I-)5. Energy optimisations indicate that the probable structures have the halide ions dispersed in a matrix of cations, which, for Bu4N+, can be mutually attractive. The aggregates are structurally fluid, with multiple structures separated by 4-8 kJmol(-1). The energy calculations are entirely consistent with the observed formation of large aggregates, and of multiply charged anions. It is estimated that the cohesive energies of supramolecular assemblies of ions such as these reach about 40 kJmol(-1) per constituent ion.

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Section: Mass Spectrometric Methodsmentioning

confidence: 99%

Supramolecular Assemblies of Quaternary Ammonium Cations and Halide Anions in the Gas Phase: ESMS-FTICR Data and Computer Modelling

Hasselgren¹,

Fisher²,

Jagner³

et al. 2000

Chem. Eur. J.

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“…Copper and halide combine in a variety of stoichiometries to form anionic complexes CuyXz, z > y (Jagner & Helgesson, 1991). The number of larger discrete (nonpolymeric) complexes with 3 < y < 56 that have been identified by single-crystal X-ray diffraction are more notable for their differences than for their similarities.…”

Section: Commentmentioning

confidence: 99%

Tris(trimethylphenylammonium) hexaiodotricuprate(I)

Hu¹,

Holt²

1994

Acta Crystallogr C

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“…The Cl À and Br À ligands provide no steric restriction to threecoordination, and the analogous three-coordinate halocuprate(i) complexes are well known. [6] Two crystalline compounds were characterised, both with the [Ph 3 PNPPh 3 ] ion, [7] namely, (Ph 3 PNPPh 3 Cl 2.4 Br 0.6 ] À (2). The three coordination is unambiguous, as there is no other donor atom within 6.7 ä of the Cu centre.…”

Section: Introductionmentioning

confidence: 99%

Three-Coordinate [CuIIX3]− (X=Cl, Br), Trapped in a Molecular Crystal

2002

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Mixtures of [Ph3PNPPh3]+Cl− with CuBr2 (or CuBr2+CuCl2) in ethanol/dichloromethane yield crystals containing three‐coordinate copper(II) with mixed chloride and bromide ligands, namely [Ph3PNPPh3]+[CuCl0.9Br2.1]− (1) and [Ph3PNPPh3]+[CuCl2.4Br0.6]− (2). The trigonal‐planar coordination of copper(II) is angularly distorted but unambiguous, as there is no other halide ligand within 6.7 Å of the copper atom. Density functional theory (DFT) calculations on planar [CuClBr2]− show that the energy surface for angle bending is very soft. Crystallisation in the presence of CH3CN yields [Ph3PNPPh3]+[CuCl0.7Br2.3(NCCH3)]− (3), in which there is additional secondary coordination by NCCH3 (Cu−N 2.44 Å). DFT calculations of the potential energy surface for this secondary coordination show that it is remarkably flat (<3 kcal mol−1 for a variation of Cu−N by 0.8 Å). The crystal packing in 1, 2 and 3, which involves multiple phenyl embraces between [Ph3PNPPh3]+ ions and numerous C−H⋅⋅⋅Cl and C−H⋅⋅⋅Br motifs, is associated with intermolecular energies that are larger than the variations in intramolecular energies. For reference, the crystal structures of [Ph3PNPPh3+]2[Cu2Cl6]2− (4) and [Ph3PNPPh3+]2[Cu2Br6]2− (5) are described. We conclude 1) that three‐coordinate copper(II) with monatomic halide ligands, although uncommon, can be regarded as normal, 2) that steric control by ligands is not necessary to enforce three‐coordination, 3) that a hydrophobic aryl environment stabilises [Cu(Cl/Br)3]−, and 4) that the energy change in the transition from three‐ to four‐coordinate copper(II) is very small (ca 5 kcal mol−1).

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On the Coordination Number of the Metal in Crystalline Halogenocuprates(I) and Halogenoargentates(I)

Cited by 103 publications

References 149 publications

Supramolecular Assemblies of Quaternary Ammonium Cations and Halide Anions in the Gas Phase: ESMS-FTICR Data and Computer Modelling

Supramolecular Assemblies of Quaternary Ammonium Cations and Halide Anions in the Gas Phase: ESMS-FTICR Data and Computer Modelling

Tris(trimethylphenylammonium) hexaiodotricuprate(I)

Three-Coordinate [CuIIX3]− (X=Cl, Br), Trapped in a Molecular Crystal

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