Joint spectroscopic and theoretical investigations of transition metal complexes involving non-innocent ligands

Ray, Kallol; Petrenko, Taras; Wieghardt, Karl; Neese, Frank

doi:10.1039/b700096k

Cited by 312 publications

(278 citation statements)

References 88 publications

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“…Likewise to C1 and C3, the Sn-N imine bond is shorter than the Sn-N qu bond (2.142(3) vs. 2.223(3)Å). The C cat -O bond lengths (1.331(4) -1.370(5)Å) are in good agreement with C-O single bond lengths in other catecholate complexes [24].…”

Section: Synthesis and Molecular Structures Of Hybrid Guanidine Tin Csupporting

confidence: 67%

Novel Tin(IV) Complexes with the Hybrid Guanidine Ligand DMEGqu

Jesser

Vieira

Herres‐Pawlis

2013

Zeitschrift Für Naturforschung B

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Novel Sn(IV) complexes with the guanidine-quinoline hybrid ligand DMEGqu are reported. With SnCl 4 , SnBr 4 , Me 2 SnCl 2 , Me 2 SnBr 2 , and the 3,5-di-tert-butyl-catecholate coligand complexes with different donor sets were synthesized. Four of these tin compounds have been modelled by density functional theory. Additionally, a tetranuclear Sn(IV) oxocluster with a novel structure motif, a distorted hetero-adamantane with bridging oxido and hydroxido ligands, is presented.

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Section: Synthesis and Molecular Structures Of Hybrid Guanidine Tin Csupporting

confidence: 67%

Novel Tin(IV) Complexes with the Hybrid Guanidine Ligand DMEGqu

Jesser

Vieira

Herres‐Pawlis

2013

Zeitschrift Für Naturforschung B

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“…Its calculated spectrum, which appeared blue-shifted by ∼0.25 eV, revealed a minor MLCT component in these bands. The TDDFT study permitted a tentative identification of d-d bands at ∼18 000 and 25 000 cm Figure 3 indicates that smif may be redox-active [7][8][9][10][11][12] in the case of 2. For 1, nonbonding, carbon-based azaallyl orbitals are the HOMO and HOMO-1.…”

mentioning

confidence: 99%

Unusual Electronic Features and Reactivity of the Dipyridylazaallyl Ligand: Characterizations of (smif)₂M [M = Fe, Co, Co⁺, Ni; smif = {(2-py)CH}₂N] and [(TMS)₂NFe]₂(smif)₂

et al. 2009

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Application of the dipyridylazaallyl ligand (2-py)CHNCH(2-py) (smif) to a series of first-row transition metals afforded (smif)2M n [n = 0, M = Fe (1), Co (2), Ni (3); n = +1, M = Co (2+)] and {(TMS)2NFe}2(smif)2 (4 2 ) via metathetical procedures. The Mössbauer spectrum of 1 (S = 0) and TDDFT calculations, including a UV−vis spectral simulation, reveal it to be a covalent, strong-field system with Δo estimated as ∼18 000 cm−1 and B ≈ 470 cm−1. (smif)2Co (2) has S = 1/2 according to SQUID data at 10 K. DFT calculations suggest that the odd electron is localized in a smif π* orbital, i.e., smif is redox-active. EPR-silent (smif)2Ni (3) has S = 1 (SQUID), and calculations show that the unpaired spins reside in the d z 2 and d x 2 −y 2 orbitals. X-ray structural parameters suggest that low-spin d6 1 and 2+ are relatively symmetric D 2d species, but 2 and 3 manifest a distortion in which one smif is canted in the plane perpendicular to the other. (smif)FeN(TMS)2 (4) is principally monomeric in solution, but reversibly dimerizes (K eq ≈ 10−4 M−1) via C−C bond formation in the azaallyl backbone to crystallize as {(TMS)2NFe}2(smif)2 (4 2 ). The azaallyl compounds possess extraordinary UV−vis absorptivities (ε ≈ 18000−52000) at 580 ± 15 nm and 406(25) nm that have been identified as intraligand bands with Cnb → smif π* character.

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“…[3,7,10,11]) and to investigate biological or biomimetic systems containing transition metal centers (see, e.g., Refs. [12][13][14][15][16][17][18]). Usually, XAS and XES are used as fingerprint techniques in such studies to identify the oxidation state, spin state, and local coordination environment of a metal center.…”

Section: Introductionmentioning

confidence: 99%

Origin-independent calculation of quadrupole intensities in X-ray spectroscopy

Bernadotte

Atkins

Jacob

2012

The Journal of Chemical Physics

147

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For electronic excitations in the ultraviolet and visible range of the electromagnetic spectrum, the intensities are usually calculated within the dipole approximation, which assumes that the oscillating electric field is constant over the length scale of the transition. For the short wavelengths used in hard X-ray spectroscopy, the dipole approximation may not be adequate. In particular, for metal K-edge X-ray absorption spectroscopy (XAS), it becomes necessary to include higher-order contributions. In quantum-chemical approaches to X-ray spectroscopy, these socalled quadrupole intensities have so far been calculated by including contributions depending on the square of the electric-quadrupole and magnetic-dipole transition moments. However, the resulting quadrupole intensities depend on the choice of the origin of the coordinate system. Here, we show that for obtaining an originindependent theory, one has to include all contributions that are of the same order in the wave vector consistently. This leads to two additional contributions depending on products of the electric-dipole andelectric-octupole and of the electric-dipole and magnetic-quadrupole transition moments, respectively. We have implemented such an origin-independent calculation of quadrupole intensities in XAS within timedependent density-functional theory, and demonstrate its usefulness for the calculation of metal and ligand K-edge XAS spectra of transition metal complexes.2

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Joint spectroscopic and theoretical investigations of transition metal complexes involving non-innocent ligands

Cited by 312 publications

References 88 publications

Novel Tin(IV) Complexes with the Hybrid Guanidine Ligand DMEGqu

Novel Tin(IV) Complexes with the Hybrid Guanidine Ligand DMEGqu

Unusual Electronic Features and Reactivity of the Dipyridylazaallyl Ligand: Characterizations of (smif)₂M [M = Fe, Co, Co⁺, Ni; smif = {(2-py)CH}₂N] and [(TMS)₂NFe]₂(smif)₂

Origin-independent calculation of quadrupole intensities in X-ray spectroscopy

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Joint spectroscopic and theoretical investigations of transition metal complexes involving non-innocent ligands

Cited by 312 publications

References 88 publications

Novel Tin(IV) Complexes with the Hybrid Guanidine Ligand DMEGqu

Novel Tin(IV) Complexes with the Hybrid Guanidine Ligand DMEGqu

Unusual Electronic Features and Reactivity of the Dipyridylazaallyl Ligand: Characterizations of (smif)2M [M = Fe, Co, Co+, Ni; smif = {(2-py)CH}2N] and [(TMS)2NFe]2(smif)2

Origin-independent calculation of quadrupole intensities in X-ray spectroscopy

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Unusual Electronic Features and Reactivity of the Dipyridylazaallyl Ligand: Characterizations of (smif)₂M [M = Fe, Co, Co⁺, Ni; smif = {(2-py)CH}₂N] and [(TMS)₂NFe]₂(smif)₂