Electronic structure of [Ni(II)S4] complexes from S K-edge X-ray absorption spectroscopy

Queen, Matt S.; Towey, Bradley; Murray, Kevin; Veldkamp, Brad S.; Byker, Harlan J.; Szilágyi, Róbert K.

doi:10.1016/j.ccr.2012.07.020

Cited by 35 publications

(53 citation statements)

References 108 publications

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“…This is the same situation as observed for the systematic evaluation of S-based ligands [91]. The energy shift of the most intense excitation correlates with the higher effective nuclear charge and the considerable lower basicity of the aromatic ligand than the aliphatic phosphane (pKa in acetonitrile 7.6-8.8 and 15.5-16.6, respectively [92]).…”

Section: P K-edge Measurementsmentioning

confidence: 62%

“…Even if we consider an adjustment to the Ni d-manifold to shift the pre-edge features higher in energy, we cannot shift and scale the calculated XAS spectrum to match both the reference and NO complexes. This is yet another indication for the challenge of describing the electronic structure of the studied Ni-NO complexes and corresponding reference compounds with DFT, which has already been emphasized for a series of [NiS 4 ] complexes [91].…”

Section: Simulated Core Level Excited State Spectramentioning

confidence: 91%

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Distorted tetrahedral nickel-nitrosyl complexes: spectroscopic characterization and electronic structure

et al. 2016

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The linear nickel-nitrosyl complex [Ni(NO)(L3)] supported by a highly hindered tridentate nitrogen-based ligand, hydrotris(3-tertiary butyl-5-isopropyl-1-pyrazolyl)borate (denoted as L3), was prepared by the reaction of the potassium salt of the ligand with the nickel-nitrosyl precursor [Ni(NO)(Br)(PPh 3 ) 2 ]. The obtained nitrosyl complexes as well as the corresponding chlorido complexes [Ni(NO)(Cl)(PPh 3 ) 2 ] and [Ni(Cl)(L3)] were characterized by X-ray crystallography and different spectroscopic methods including IR/far-IR, UV-Vis, NMR, and multi-edge X-ray absorption spectroscopy at the Ni K-, Ni L-, Cl K-, and P K-edges. For comparative electronic structure analysis we also performed DFT calculations to further elucidate the electronic structure of [Ni(NO)(L3)]. These results provide the nickel oxidation state and the character of the Ni-NO bond. The complex [Ni(NO)(L3)] is best described as [Ni (II) (NO (-) )(L3)], and the spectroscopic results indicate that the phosphane complexes have a similar [Ni (II) (NO (-) )(X)(PPh 3 ) 2 ] ground state.

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Section: P K-edge Measurementsmentioning

confidence: 62%

Section: Simulated Core Level Excited State Spectramentioning

confidence: 91%

Distorted tetrahedral nickel-nitrosyl complexes: spectroscopic characterization and electronic structure

et al. 2016

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“…The pre-edge features at the sulfur and chlorine K-edges below the ionization threshold appear to be due to a mixing of the vacant Bi 6p orbitals with the filled 3p donor orbitals of the S and Cl ligands. The rising-edge features superimposed on the ionization edge-jump for the Tm tBu ligand are informative about changes in the S-C bonding (Queen et al, 2013). The appearance of multiple preedge features at the Cl K-edge is indicative of the different chemical environments of the terminal and bridging chloride ligands (Barton et al, 2015).…”

Section: Figurementioning

confidence: 98%

“…Relativistic effects were considered by requesting molecular integral evaluations employing the Douglas-Kroll-Hess 4th order relativistic correction including spin-orbit terms. The connection between the experimental and calculated Bi-S/Cl bond covalency was derived using the transition dipole expression (Solomon et al, 2005), as detailed in Barton et al (2015) and Queen et al (2013). The H-atom positions for the sodium salt of the Tm tBu anion and complexes (I) and (II) were refined by structural optimizations.…”

Section: Refinementmentioning

confidence: 99%

“…The individual fits with the least number of Gaussian/Lorentzian amplitude functions were determined from the number of resolved peaks from the second derivative spectra (see Supporting information). The conversion of spectral intensities to orbital compositions was carried out as described earlier for terminal and bridging chloride (Barton et al, 2015) and sulfur ligands (Queen et al, 2013).…”

Section: Refinementmentioning

confidence: 99%

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Mono- and binuclear tris(3-tert-butyl-2-sulfanylidene-1H-imidazol-1-yl)hydroborate bismuth(III) dichloride complexes: a soft scorpionate ligand can coordinate top-block elements

et al. 2016

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Tris(pyrazolyl)hydroborate ligands have been utilized in the fields of inorganic and coordination chemistry due to the ease of introduction of steric and electronic substitutions at the pyrazole rings. The development and use of the tris(pyrazolyl)hydroborate ligand, called a `scorpionate', were pioneered by the late Professor Swiatoslaw Trofimenko. He developed a second generation for his ligand system by the introduction of 3-tert-butyl and 3-phenyl substituents and this new ligand system accounted for many remarkable developments in inorganic and coordination chemistry in stabilizing monomeric species while maintaining an open coordination site. Bismuth is remarkably harmless among the toxic heavy metal p-block elements and is now becoming popular as a replacement for highly toxic metal elements, such as lead. Two bismuth(III) complexes of the anionic sulfur-containing tripod tris(3-tert-butyl-2-sulfanylidene-1H-imidazol-1-yl)hydroborate ligand were prepared. By recrystallization from MeOH/CHCl, orange crystals of dichlorido(methanol-κO)[tris(3-tert-butyl-2-sulfanylidene-1H-imidazol-1-yl-κS)hydroborato]bismuth(III), [Bi(CHBNS)Cl(CHO)], (I), were obtained, manifesting a mononuclear structure. By using a noncoordinating solvent, red crystals of the binuclear structure with bridging Cl atoms were obtained, namely di-μ-chlorido-bis{chlorido[tris(3-tert-butyl-2-sulfanylidene-1H-imidazol-1-yl-κS)hydroborato]bismuth(III)}, [Bi(CHBNS)Cl], (II). These complexes show {BiSClO} and {BiSCl} coordination geometries with average Bi-S bond lengths of 2.73 and 2.78 Å in (I) and (II), respectively. The overall Bi coordination geometry is distorted octahedral due to stereochemically active lone pairs. The three Bi-S bond lengths are almost equal in (I) but show considerable differences in (II), with one long and two shorter distances that also correlate with changes in the UV-Vis and H NMR spectra. For direct measurements of the Bi-S/Cl coordination, ligand K-edge X-ray absorption measurements were carried out in combination with ground and excited-state electronic structure analyses. For p-block elements, these sulfur-containing ligands are useful for preparing the appropriate complexes due to their flexible coordination geometry.

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Quantifying the Interdependence of Metal–Ligand Covalency and Bond Distance Using Ligand K‐edge XAS

et al. 2019

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Bond distance is acommon structural metric used to assess changes in metal-ligand bonds,b ut it is not clear how sensitive changes in bond distances are with respect to changes in metal-ligand covalency.Here we report ligand K-edge XAS studies on Ni and Pd complexes containing different phosphorus(III) ligands.D espite the large number of electronic and structural permutations,PK-edge pre-edge peak intensities reveal ar emarkable correlation that spectroscopically quantifies the linear interdependence of covalent MÀP s bonding and bond distance.ClK-edge studies conducted on many of the same Ni and Pd compounds revealed ap oor correlation between M À Cl bond distance and covalency, but as trong correlation was established by analyzing Cl K-edge data for Ti complexes with aw ider range of Ti À Cl bond distances.T ogether these results establish aquantitative framework to begin making more accurate assessments of metalligand covalency using bond distances from readily-available crystallographic data.Supportinginformation and the ORCID identification number(s) for the author(s) of this article can be found under: https://doi.

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Electronic structure of [Ni(II)S4] complexes from S K-edge X-ray absorption spectroscopy

Cited by 35 publications

References 108 publications

Distorted tetrahedral nickel-nitrosyl complexes: spectroscopic characterization and electronic structure

Distorted tetrahedral nickel-nitrosyl complexes: spectroscopic characterization and electronic structure

Mono- and binuclear tris(3-tert-butyl-2-sulfanylidene-1H-imidazol-1-yl)hydroborate bismuth(III) dichloride complexes: a soft scorpionate ligand can coordinate top-block elements

Quantifying the Interdependence of Metal–Ligand Covalency and Bond Distance Using Ligand K‐edge XAS

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