Crystal Structure and Electronic and Magnetic Properties of Hexacyanoosmate(III)

Alborés, Pablo; Slep, Leonardo D.; Baraldo, Luis M.; Baggio, Ricardo; Garland, Marı́a Teresa; Rentschler, Eva

doi:10.1021/ic0516818

Cited by 44 publications

(78 citation statements)

References 19 publications

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“…This is not so. As recently discussed by Slep and coworkers, 63 the best approach for analyzing magnetic or EPR data even for such an S = 1/2 system is by a complete ligand-field analysis using the entire d 5 64,65 The many pitfalls of extracting electronic configuration from the observed g values, such as their assignment to g x , g y , g z , are clearly explained in these papers. We will reproduce one such set of equations from one of McGarvey's papers, namely for tetragonally distorted LS d 5 , with the real d orbital basis set.…”

Section: Resultsmentioning

confidence: 99%

“…In further contrast to Cu(OEP) (Figure 1), the equatorial 5 is best exemplified by Fe III with strong-field ligands (e.g., tetrapyrroles yet again, but also with strong axial ligands), and also by complexes of the other Group 8 ions, Ru III 25,62 and Os III . 63 The electronic configuration d 5 has the largest number of microstates (252) and the most complicated electronic energy levels for the free-ion. The LS d 5 state (t 2 5 configuration) might seem to elude this complication and be as easily understood as d 9 is.…”

Section: Resultsmentioning

confidence: 99%

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A perspective on applications of ligand-field analysis: inspiration from electron paramagnetic resonance spectroscopy of coordination complexes of transition metal ions

Telser¹

2006

J. Braz. Chem. Soc.

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Este artigo descreve de maneira um tanto pessoal, o uso da espectroscopia de ressonância paramagnética eletrônica (EPR), incluindo EPR de alta freqüência e alto campo (HFEPR) para investigar a estrutura eletrônica de complexos de íons de metal de transição. Os parâmetros Hamiltonianos de spin, obtidos a partir de experimentos EPR, matriz g para sistemas com S =1/2 e matrizes g e D (zero-field splitting) para sistemas com S > 1/2 fornecem informações sobre os níveis de energia dos orbitais d. Esta informação pode ser combinada com a teoria do campo ligante (TCL) para fornecer informações a respeito da estrutura eletrônica global de complexos paramagnéticos de metal de transição. Como tem sido discutido por outros autores a TCL ainda se mostra útil para o entendimento quantitativo destes complexos, mesmo com a atual disponibilidade de métodos computacionais avançados, como a teoria do funcional de densidade (DFT). A discussão é ilustrada por exemplos ao longo da série de transição, com configurações d n . This paper describes in a somewhat personal way an overview of the use of electron paramagnetic resonance (EPR) spectroscopy, including high-frequency and -field EPR (HFEPR) to unravel the electronic structure of transition metal ion complexes. The spin Hamiltonian parameters obtained from EPR experiments, namely the g matrix for systems with S =1/2 and the g and D (zero-field splitting) matrices for systems with S > 1/2 provide information on d orbital energy levels. This information can be combined with ligand-field theory (LFT) to provide information on the overall electronic structure of the paramagnetic transition metal complex. As has been discussed by others, LFT is still useful in providing such a quantitative understanding of these complexes, even in the day of advanced computational methods, such as density functional theory (DFT). The discussion is illustrated by examples across the d n configuration.

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Section: Resultsmentioning

confidence: 99%

Section: Resultsmentioning

confidence: 99%

A perspective on applications of ligand-field analysis: inspiration from electron paramagnetic resonance spectroscopy of coordination complexes of transition metal ions

Telser¹

2006

J. Braz. Chem. Soc.

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“…If the hexacyanoosmate(II) was known for a long time [42], its crystal structure having been determined for the sodium salt Na 4 [Os II (CN) 6 ]·10H 2 O [28], the paramagnetic hexacyanoosmate(III) was only recently structurally characterized and magnetically investigated as Ph 4 P + salt [30] despite the successful synthesis of n-Bu 4 N analog almost 50 years ago [43]. Both paramagnetic cyanides were prepared starting from the diamagnetic precursor K 4 …”

Section: Synthesis and Characterizationmentioning

confidence: 99%

“…The axial atoms are slightly tilted with respect to the equatorial plane; the maximal distortion is~4 • . The Os-C distances fall within the range of 2.046(7)-2.093(7) Å and the apical Os-C distances vary in the range of 2.043 (8) characterized and magnetically investigated as Ph4P + salt [30] despite the successful synthesis of n-Bu4N analog almost 50 years ago [43]. Both paramagnetic cyanides were prepared starting from the diamagnetic precursor K4[Os II (CN)6]·3H2O.…”

Section: Crystal Structure Descriptionmentioning

confidence: 99%

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The First Homoleptic Complex of Seven-Coordinated Osmium: Synthesis and Crystallographical Evidence of Pentagonal Bipyramidal Polyhedron of Heptacyanoosmate(IV)

2016

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Abstract:The ligand exchange in (n-Bu 4 N) 2 Os IV Cl 6 (n-Bu 4 N = tetra-n-butylammonium) leads to the formation of the osmium(IV) heptacyanide, the first fully inorganic homoleptic complex of heptacoordinated osmium. The single-crystal X-ray diffraction (SC-XRD) study reveals the pentagonal bipyramidal molecular structure of the [Os(CN) 7 ] 3− anion. The latter being a diamagnetic analogue of the highly anisotropic paramagnetic synthon, [Re IV (CN) 7 ] 3− can be used for the synthesis of the model heterometallic coordination compounds for the detailed study and simulation of the magnetic properties of the low-dimensional molecular nanomagnets involving 5d metal heptacyanides.

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Spin‐Orbit Coupling: Effects in Heavy Element Chemistry

Kaltsoyannis

2005

Encyclopedia of Inorganic Chemistry

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Starting from the premise that the chemical consequences of scalar relativistic effects are by now largely understood, and may be incorporated more or less routinely into quantum chemical calculations, this contribution focuses on the historically less widely investigated part that spin‐orbit coupling plays in heavy element electronic structure. The effects of relativity are first summarized, followed by a discussion of the principal approaches to the calculation of molecular electronic structure and how relativistic effects may be incorporated into them. Two approaches for the calculation of spin‐orbit coupling effects are then presented; namely, the spin‐orbit coupled time‐dependent density functional theory technique of Wang et al . [Wang, F.; Ziegler, T.; van Lenthe, E.; van Gisbergen, S.; Baerends, E. J. J. Chem. Phys. 2005 , 122 , 204103] and the spin‐orbit restricted active space state interaction method of Roos and coworkers [Roos, B. O.; Malmqvist, P. A. Phys. Chem. Chem. Phys. 2004 , 6 , 2919]. Recent applications of both approaches to the electronic structure of p, d, and f block systems are then discussed, with emphasis on the improved understanding and agreement with experiment that these methods yield.

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Crystal Structure and Electronic and Magnetic Properties of Hexacyanoosmate(III)

Cited by 44 publications

References 19 publications

A perspective on applications of ligand-field analysis: inspiration from electron paramagnetic resonance spectroscopy of coordination complexes of transition metal ions

A perspective on applications of ligand-field analysis: inspiration from electron paramagnetic resonance spectroscopy of coordination complexes of transition metal ions

The First Homoleptic Complex of Seven-Coordinated Osmium: Synthesis and Crystallographical Evidence of Pentagonal Bipyramidal Polyhedron of Heptacyanoosmate(IV)

Spin‐Orbit Coupling: Effects in Heavy Element Chemistry

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