Fluorosulfates of palladium

1977 ◽  
Vol 55 (13) ◽  
pp. 2473-2477 ◽  
Author(s):  
K. C. Lee ◽  
F. Aubke
Keyword(s):  
Ground State ◽  
Diffuse Reflectance ◽  
Magnetic Measurements ◽  
Structural Information ◽  
Tridentate Ligand ◽  
Ligand Field ◽  
Polymeric Structure ◽  
Octahedral Environment ◽  
Fluorosulfate Group ◽  
Ligand Field Parameter

The syntheses of Pd(SO3F)2 and Pd(SO3F)3 by the reactions of palladium with BrOSO2F and S2O6F2 are described. Structural information on both compounds is based on infrared, Raman, diffuse reflectance, and electronic mull spectra as well as magnetic measurements from ∼300 to ∼100 K. Palladium bisfluorosulfate is found to have a polymeric structure with the fluorosulfate group acting as a tridentate ligand. As a consequence, an octahedral environment is found for Pd2+ with a 3A2g ground state, a µeff298 value of 3.39 BM and the ligand field parameter Dq = 1177 cm−1 and B = 633 cm−1. Pd(SO3F)3 is best regarded as PdII[PdIV(SO3F)6].

The Ground State in Tris(acetylacetonato)ruthenium(III) from Low-Temperature Single-Crystal Magnetic Properties

1998 ◽  
Vol 51 (3) ◽  
pp. 229 ◽  
Author(s):  
Philip A. Reynolds ◽  
Brian N. Figgis ◽  
Boujemaa Moubaraki ◽  
Keith S. Murray
Keyword(s):  
Ground State ◽  
Field Model ◽  
Ligand Field ◽  
Spin Orbit Coupling ◽  
Coupling Constant ◽  
Magnetic Exchange Interaction ◽  
Magnetic Exchange ◽  
Structural Details ◽  
Ligand Field Parameter ◽  
Good Agreement

The magnetic susceptibilities of tris(acetylacetonato)ruthenium(III) have been measured between 2·5 and 300 K along the a, b, c, and a* axis directions, together with the magnetizations along the same directions up to a magnetic field of 5 T. There is a small amount of magnetic exchange interaction apparent below 10 K, with Weiss constants up to –0·35 K and the magnetization is fitted with exchange integrals up to –0·38 K in magnitude. A pathway for magnetic exchange in terms of a pair of symmetry-related Ru(acac) rings lying parallel and close is obvious from the structure. The susceptibility results above 10 K have been interpreted in terms of a four-parameter ligand field model (CF1) operating on the ground 2T2g term of the d5 configuration. The t2g orbitals are found to be split by 475 cm-1 by a dominant trigonal symmetry component and then by –50 cm-1 by a subsidiary rhombic component. The single-electron spin-orbit coupling constant is 875 cm-1 and the orbital angular momentum reduction parameter is 0·7. The g-values deduced for the ground Kramers doublet are not in good agreement with those from e.s.r. experiments, but rather better agreement is found for closely allied ligand field parameter sets (CF2) which can fit the susceptibilities at particular temperatures but do not reproduce their temperature dependence well. Consideration of the variation of structural details with temperature indicate that, in fact, the CF2 sets may be more realistic.

Fluorosulfates of palladium. Part 2. The hexakis(fluorosulfato)palladate (IV)ion and palladium(II) hexakis(fluorosulfato)metallates(IV)

1979 ◽  
Vol 57 (15) ◽  
pp. 2058-2064 ◽  
Author(s):  
Keith C. Lee ◽  
Friedhelm Aubke
Keyword(s):  
Vibrational Spectra ◽  
Ground State ◽  
Ligand Field ◽  
Octahedral Environment ◽  
Ligand Field Parameters

The synthesis of a number of compounds containing the hexakis(fluorosulfato)palladate(IV) anion and the cations Cs+, Ba2+,NO+, and ClO2+ is reported. All compounds are diamagnetic. Also reported is the synthesis of Pd[M(SO3F)6], where M = Pt(IV) and Sn(IV). Here, palladium(II) is found in a regular octahedral environment. Both compounds are paramagnetic, consistent with a 3A2g ground state. Curie–Weiss law behavior is found and ligand field parameters for the Pd(II) derivatives are reported. Vibrational spectra are reported for all new fluorosulfato complexes.

Transition metal complexes of 6-amino 2-thiouracil; crystal structure of bis(6-amino-2-thiouracilato)aquazinc(II) dihydrate

1993 ◽  
Vol 71 (1) ◽  
pp. 29-33 ◽  
Author(s):  
M. Angustias Romero ◽  
M. Purificación Sánchez ◽  
Miguel Quirós ◽  
Francisco Sánchez ◽  
Juan Manuel Salas ◽  
...  
Keyword(s):  
Crystal Structure ◽  
Transition Metal Complexes ◽  
Diffuse Reflectance ◽  
Zinc Complex ◽  
Magnetic Measurements ◽  
Chelate Ring ◽  
X Ray Diffraction ◽  
X Ray ◽  
Octahedral Environment ◽  
Distorted Octahedral

Complexes of 6-amino-2-thiouracil (H2ATU) with the metal ions Ni(II), Co(II), Zn(II), Cd(II), Cu(I), Ag(I), and Hg(II) have been isolated and characterized by means of elemental analysis, infrared, NMR, and visible spectroscopies, and magnetic measurements. The crystal structure of [Zn(HATU)2(H2O)] • 2H2O has been solved by X-ray diffraction showing that the metal atom is five-coordinated by a water molecule and two ligands that bind through the sulphur and N1 atoms, closing a four-member chelate ring. Diffuse reflectance spectra and magnetic measurements suggest that [Co(HATU)2(H2O)] • 2H2O has a similar structure to that of the zinc complex, and that the nickel complexes [Ni(HATU)2] and [Ni(HATU)2(H2O)2] have, respectively, a tetrahedral and a D4h-distorted octahedral environment.

scholarly journals A polymeric oxovanadium(IV) pyromellitate complex

1999 ◽  
Vol 64 (9) ◽  
pp. 513-518
Author(s):  
Dusanka Vasovic ◽  
Djordje Stojakovic
Keyword(s):  
Ir Spectroscopy ◽  
Potassium Carbonate ◽  
Magnetic Measurements ◽  
Antiferromagnetic Coupling ◽  
Polymeric Complex ◽  
Pyromellitic Acid ◽  
Polymeric Structure

The reaction of oxovanadium(IV) sulphate with 1,2,4,5-benzenetetracarboxylic acid (pyromellitic acid) in the presence of potassium carbonate yields a polymeric complex, K2[VO(pyr)]-6H2O (I) [pyr = pyromellitate(4-) ion]. The PM3(tm) calculations and IR spectroscopy suggest that the polymeric structure of I consists of ?V-pyr-V-pyr- chains formed by the 1,4- or 1,5-bridging by the pyr ions. The chains are additionally cross-linked by the chelate function of one of the COO. groups of the pyr ion. Magnetic measurements do not reveal the presence of antiferromagnetic coupling between the V centers.

Über die Natur der Cu2+-Zentren im NH4Cl - die spektroskopische Untersuchung von Cu2+-dotiertem Hg(NH3)2Cl2/The Nature of the Cu2+ Centres in NH4Cl - a Spectroscopic Investigation of Cu2+ Doped Hg(NH3)2Cl2

1992 ◽  
Vol 47 (4) ◽  
pp. 465-469 ◽  
Author(s):  
G. Steffen ◽  
U. Kaschuba ◽  
M. A. Hitchman ◽  
D. Reinen
Keyword(s):  
Ground State ◽  
Spectroscopic Investigation ◽  
Reflectance Spectra ◽  
Ligand Field ◽  
Field Reflectance

The preparation of Hg(NH3)2Cl2 doped with a small amount of Cu2+ is reported. The EPR and ligand field reflectance spectra indicate the presence of “CuCl4(NH3)2” polyhedra with a compressed tetragonal geometry and confirm, that the centres in Cu2+ doped NH4Cl possess the same geometry - as postulated earlier. The Cu2+ centres in Hg(NH3)2Cl2 are less compressed than those in NH4Cl, however, as could be deduced from the copper(II) hyperfine values, which are strongly influenced by the quite different admixture of the metal 4s orbital into the Alg (dz2) ground state in the two cases, and from the comparable energies of the d - d transitions.

Magnetism, electronic spectra, and structure of transition metal alkoxides. I. methoxides and ethoxides of chromium(II), manganese(II), Iron(II), cobalt(II), nickel(II), copper(II), titanium(III), chromium(III), and iron(III)

1966 ◽  
Vol 19 (2) ◽  
pp. 207 ◽  
Author(s):  
RW Adams ◽  
E Bishop ◽  
RL Martin ◽  
G Winter
Keyword(s):  
Transition Metal ◽  
Spectral Data ◽  
Electronic Spectra ◽  
Magnetic Moments ◽  
Field Parameter ◽  
Ligand Field ◽  
Metal Alkoxides ◽  
Infinite Lattices ◽  
Ligand Field Parameter

The magnetic moments and electronic spectra are reported for the following divalent transition metal methoxides: Cr(OCH3)2, Mn(OCH3)2, Fe(OCH3)2, Co(OCH3)2, Ni(OCH3)2, and Cu(OCH3)2. These measurements when coupled with the involatility and insolubility of the compounds favour structures based on infinite lattices composed either of regular (Mn, Fe, Co, and Ni) or distorted (Cr and Cu) MO6 octahedra. The spectral data place the ligand field parameter, Δ, for the methoxide group very close to that of water.

scholarly journals Ligand field parameters and the ground state of Fe(II) phthalocyanine

2013 ◽  
Vol 138 (24) ◽  
pp. 244308 ◽  
Author(s):  
M. D. Kuz'min ◽  
A. Savoyant ◽  
R. Hayn
Keyword(s):  
Ground State ◽  
Ligand Field ◽  
Ligand Field Parameters

A linear cobalt(II) complex with maximal orbital angular momentum from a non-Aufbau ground state

Science ◽  
2018 ◽  
Vol 362 (6421) ◽  
pp. eaat7319 ◽  
Author(s):  
Philip C. Bunting ◽  
Mihail Atanasov ◽  
Emil Damgaard-Møller ◽  
Mauro Perfetti ◽  
Iris Crassee ◽  
...  
Keyword(s):  
Magnetic Susceptibility ◽  
Angular Momentum ◽  
Orbital Angular Momentum ◽  
Ground State ◽  
Dominant Role ◽  
Far Infrared ◽  
Wave Number ◽  
Ligand Field ◽  
Electron Configuration ◽  
Susceptibility Data

Orbital angular momentum is a prerequisite for magnetic anisotropy, although in transition metal complexes it is typically quenched by the ligand field. By reducing the basicity of the carbon donor atoms in a pair of alkyl ligands, we synthesized a cobalt(II) dialkyl complex, Co(C(SiMe2ONaph)3)2 (where Me is methyl and Naph is a naphthyl group), wherein the ligand field is sufficiently weak that interelectron repulsion and spin-orbit coupling play a dominant role in determining the electronic ground state. Assignment of a non-Aufbau (dx2–y2, dxy)3(dxz, dyz)3(dz2)1 electron configuration is supported by dc magnetic susceptibility data, experimental charge density maps, and ab initio calculations. Variable-field far-infrared spectroscopy and ac magnetic susceptibility measurements further reveal slow magnetic relaxation via a 450–wave number magnetic excited state.

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