Magnetic and spectroscopic studies of structure and bonding in hexafluorophosphate and hexafluoroarsenate complexes of copper(II)

Abstract

. Can. J. Chem. 60, 1048 (1982).Complexes of composition CuL4(EF6), (where L is pyridine, 3-methylpyridine, or 4-methylpyridine and E is P or As) have been prepared and characterized by epr, electronic and infrared spectroscopic, and magnetic susceptibility studies. Results are consistent with elongated tetragonal-octahedral structures with coordinated anions. The coordinating strength of PF6-is estimated to be less than that of AsF6-and both are considered weaker than perchlorate. Analysis of the epr data indicates significant metal to heterocyclic ligand a-electron delocalization, the extent and nature of which depends on the orientation of the heterocyclic ring in the CuL, chromophore. Analysis of infrared data suggests that the intensities of the v, and v, vibrations as they occur in EF,-complexes generally provide an indication of the strength of metal-anion interactions. Ona prepart des complexes deformule CuL,(EF,),(ou L = pyridine, methyl-3 pyridine ou mtthyl-4pyridine et E = Pou As) et on les a caractCris6 par des etudes de rpe, de spectroscopie infrarouge et de susceptibilite magnetique. Les resultats sont en accord avec des structures tktragonales-octahtdriques allongees avec des anions coordones. On Cvalue la force de coordination de PF6-comme itant inferieure a celle de AsF6-et on considkre ces deux forces plus faibles que celle du perchlorate. L'analyse des donnees de la rpe indique une delocalisation importante de I'electron a du ligand heterocyclique par rapport au metal. La nature et le taux de cette dtlocalisation dependent de I'orientation de I'hCtCrocycle dans le chromophore CuL,. L'analyse des donnees infrarouges suggtre que les intensites des vibrations v, et v, telles qu'elles se produisent dans les complexes de EF6-constituent gtneralement une indication de la force des interactions mttal-anion.[Traduit par le journal]

A copper(II)–pyrazole complex cation with \bf \overline 3 imposed symmetry

“…The corresponding bands for the PF 6 À group in (II) are observed at 840 and 561 cm À1 , respectively. These data are consistent with criteria for non-coordinating AsF 6 À or PF 6 À moieties (Morrison & Thompson, 1982).…”

“…The energy of the peak maximum in the visible spectra (15 100 cm À1 ) is comparable with those observed for other complexes containing the [CuN 6 ] 2+ chromophore (McKenzie, 1970). The IR bands for the PF 6 À and AsF 6 À moieties are assigned on the basis of data from previously characterized hexa¯uorophosphate and hexa¯uoroarsenate complexes (Morrison & Thompson, 1982). For (I), # 3 and # 4 of the AsF 6 À group are observed at 705 and 411 cm À1 , respectively, and show no splitting.…”

Anion-dependent host–guest properties of porous assemblies of coordination complexes (PACs), [Cu(A)2(py)4] (A = PF6, BF4, CF3SO3, and CH3SO3; py = pyridine), based on Werner-type copper(ii) complexes in the solid state

“…α-[Cu(PF 6 ) 2 ( py) 4 ] (α-PAC-2-PF 6 ) and α-[Cu(CF 3 SO 3 ) 2 ( py) 4 ] (α-PAC-2-CF 3 SO 3 ) were prepared according to the literature method. 18,19 α-[Cu(BF 4 ) 2 ( py) 4 ] (α-PAC-2-BF 4 ) was synthesized using a similar procedure to α-PAC-2-CF 3 SO 3 , except that the Cu(BF 4 ) 2 salt was used instead of the Cu(CF 3 SO 3 ) 2 salt. 19 α-[Cu(PF 6 ) 2 ( py) 4 ] (α-PAC-2-PF 6 ).…”

Diverse structures and adsorption properties of quasi-Werner-type copper(ii) complexes with flexible and polar axial bonds

“…8 Recently, we have succeeded in the single-crystal X-ray diffraction analysis of α-1. 7a The crystal structure of α-1 has been briefly reported in our previous literature.…”