Tellus in, Tellus out: The Chemistry of the Vanadium Bis(telluride) Functionality

Kilgore, Uriah J.; Karty, Jonathan A.; Pink, Maren; Gao, Xinfeng; Mindiola, Daniel J.

doi:10.1002/anie.200806022

Cited by 30 publications

(29 citation statements)

References 30 publications

(47 reference statements)

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“…The extruded monomer TeQCH t Bu spontaneously dimerises to give a four-membered 1,3-C 2 Te 2 ring (23), as well as the five-membered 1,2,4tritelluroalane (24) presumably formed by Te insertion. 26 The structures and reactivities of the series of chalcogen(IV) diimides E(NR) 2 (E = S, Se, Te) provide a persuasive demonstration of the relative weakness of tellurium-nitrogen p-bonding (ref. 2i, ESI †).…”

Section: Multiple Bondingmentioning

confidence: 99%

Tellurium: a maverick among the chalcogens

2015

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The scant attention paid to tellurium in both inorganic and organic chemistry textbooks may reflect, in part, the very low natural abundance of the element. Such treatments commonly imply that the structures and reactivities of tellurium compounds can be extrapolated from the behaviour of their lighter chalcogen analogues (sulfur and selenium). In fact, recent findings and well-established observations clearly illustrate that this assumption is not valid. The emerging importance of the unique properties of tellurium compounds is apparent from the variety of their known and potential applications in both inorganic and organic chemistry, as well as materials science. With reference to selected contemporary examples, this Tutorial Review examines the fundamental concepts that are essential for an understanding of the unique features of tellurium chemistry with an emphasis on hypervalency, three-centre bonding, secondary bonding interactions, σ and π-bond energies (multiply bonded compounds), and Lewis acid behaviour.

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Section: Multiple Bondingmentioning

confidence: 99%

Tellurium: a maverick among the chalcogens

2015

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“…Complexes 22-38 were synthesized by the Mindiola group; synthesis and characterization are described elsewhere (Figure 3). [45][46][47][48][49][50][51][52][53][54] Complexes 19-21 were commercially available and used without further purification. This combined dataset is the first of its kind, containing XANES data for V complexes with a wide range of local chemical environments (V-L, L = C, N, O, P, S, Cl, and Se) and oxidation states (+1, +2, +3, +4, and +5).…”

Section: Computational and Experimental Methodsmentioning

confidence: 99%

K-edge XANES Analysis for Catalytically Relevant Molecular and Supported Vanadium Complexes

Patel

Jafari

et al. 2022

Preprint

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X-ray Absorption Near-Edge Structure (XANES) spectroscopy is a powerful tool to reveal key structural and electronic features of isolated catalytic sites, yet insights into molecular structure and more detailed orbital analysis through a combination of experimental and computed XANES analysis are necessary for accurate interpretation of the spectra, especially when significant heterogeneity exits among the catalytic sites. Herein, we present an integrated computational and experimental strategy to determine both primary and secondary bonding interactions within the XANES pre-edge region for organovanadium complexes, which was developed using a series of well-defined molecular vanadium complexes and then applied to the characterization of a supported organovanadium olefin hydrogenation catalyst. Time-dependent density functional theory is used to predict the energy of pre-edge XANES features for a series of vanadium complexes with a variety of oxidation states and local coordination environments. A calibration scheme incorporating different density functionals and basis sets is established, resulting in an optimized scheme that accurately predicts pre-edge energies with a mean absolute error of 0.40 eV. Second-shell coordination (e.g., V---V) effects within XANES are identified through the analysis of the computed dominant orbital contributions for multi-vanadium complexes. Orbital analysis also provided confirmation that the vanadium-hydride formation combined with the heterogeneity of the catalytic active species in olefin hydrogenation caused the energy shift and broadening of the pre-edge peak after hydrogen treatment of the silica-supported organovanadium pre-catalyst. This work further elucidates computational XANES simulations and techniques potentially guiding characterization in surface organometallic chemistry.

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“…The IR spectrum of the reactive C 2v -symmetric molecule CS 3 has been recorded in an argon matrix. 10 Adsorption of S onto the Pd (111) surface generates an ordered S over-layer but annealing at 700 K leads to penetration of S into the surface, 11 generating a surface of identical geometry to pristine Pd (111) but with different binding affinities for H 2 . Work by Pore reported the atomic layer deposition of metal selenides and tellurides using alkylsilyl compounds of Se and Te as precursors.…”

Section: Binary Ternary and Quarternary Chalcogenidesmentioning

confidence: 99%

“…110 Reaction of [(PNP)V = CH t Bu(Te)] (PNP = N(2-P i Pr 2 -4-methylphenyl) 2 ) with excess Te yielded the first 3d transition metal bis(telluride) complex, (PNP)V(Te) 2 . 111 Variations on the E 2 2À ligand have also been explored. Reaction of 112 Reaction of S 2 Cl 2 with the triangular telluride-bridged clusters [M 3 (m 3 -Te)(m 2 -Te 2 ) 3 {(EtO) 2 PS 2 } 3 ] + (M = Mo,W) occured with Te/S exchange in the m 2 -Te 2 2À ligands to generate the novel TeS 2À ligand.…”

Section: Molecular Chalcogenide Complexesmentioning

confidence: 99%