A four-coordinate thionitrosyl complex of vanadium

Tran, Ba L.; Thompson, Richard R.; Ghosh, Soumya; Gao, Xinfeng; Chen, Chun-Hsing; Baik, Mu‐Hyun; Mindiola, Daniel J.

doi:10.1039/c3cc38799b

Cited by 16 publications

(5 citation statements)

References 29 publications

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“…Among the early transition metals, vanadium chemistry has witnessed a remarkable activity over the past 50 years and has been applied in heterogeneous and homogeneous catalysis, small molecule activation, − molecular magnetism, − and spin qubits. − Narrowing down the field to NHC vanadium complexes, since the first two reports of vanadium NHC complexes in 1994 by Roesky et al. and 2003 by Abernethy et al , the utility of these complexes has mostly been explored in polymerization catalysis. − Beyond this, only a few other applications of vanadium-NHC complexes have been examined, including small molecule activation , and the neutralization of chemical warfare agents .…”

Section: Introductionmentioning

confidence: 99%

Mesoionic Carbenes in Low- to High-Valent Vanadium Chemistry

et al. 2021

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We report the synthesis of vanadium(V) oxo complex 1 with a pincer-type dianionic mesoionic carbene (MIC) ligand L 1 and the general formula [VOCl(L 1 )]. A comparison of the structural (SC-XRD), electronic (UV–vis), and electrochemical (cyclic voltammetry) properties of 1 with the benzimidazolinylidene congener 2 (general formula [VOCl(L 2 )]) shows that the MIC is a stronger donor also for early transition metals with low d-electron population. Since electrochemical studies revealed both complexes to be reversibly reduced, the stronger donor character of MICs was not only demonstrated for the vanadium(V) but also for the vanadium(IV) oxidation state by isolating the reduced vanadium(IV) complexes [Co(Cp*) 2 ][1] and [Co(Cp*) 2 ][2] ([Co(Cp*) 2 ] = decamethylcobaltocenium). The electronic structures of the compounds were investigated by computational methods. Complex 1 was found to be a moderate precursor for salt metathesis reactions, showing selective reactivity toward phenolates or secondary amides, but not toward primary amides and phosphides, thiophenols, or aryls/alkyls donors. Deoxygenation with electron-rich phosphines failed to give the desired vanadium(III) complex. However, treatment of the deprotonated ligand precursor with vanadium(III) trichloride resulted in the clean formation of the corresponding MIC vanadium(III) complex 6 , which undergoes a clean two-electron oxidation with organic azides yielding the corresponding imido complexes. The reaction with TMS-N 3 did not afford a nitrido complex, but instead the imido complex 10 . This study reveals that, contrary to popular belief, MICs are capable of supporting early transition-metal complexes in a variety of oxidation states, thus making them promising candidates for the activation of small molecules and redox catalysis.

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Section: Introductionmentioning

confidence: 99%

Mesoionic Carbenes in Low- to High-Valent Vanadium Chemistry

et al. 2021

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“…While nitrosyl complexes of transition metals are well documented, 1 the chemistry of the heavier chalcogen analogues, namely, thionitrosyl and selenonitrosyl complexes, has received less attention [2][3][4][5][6][7][8][9][10][11][12][13][14][15][16][17][18][19][20] due, in part, to the difficulty of their preparations. Common synthetic routes to thionitrosyl complexes include (a) sulfur atom transfer to metal nitrides, (b) reaction of N 3 S 3 Cl 3 or NS + salts with metal complexes, (c) halide abstraction from thiazyl complexes, and (d) reaction of S 4 N 4 with metal halides or nitrides.…”

Section: Introductionmentioning

confidence: 99%

Ruthenium chalcogenonitrosyl and bridged nitrido complexes containing chelating sulfur and oxygen ligands

Cheung

Huang

et al. 2015

Dalton Trans.

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Ruthenium thio- and seleno-nitrosyl complexes containing chelating sulfur and oxygen ligands have been synthesised and their de-chalcogenation reactions have been studied. The reaction of mer-[Ru(N)Cl3(AsPh3)2] with elemental sulfur and selenium in tetrahydrofuran at reflux afforded the chalcogenonitrosyl complexes mer-[Ru(NX)Cl3(AsPh3)2] [X = S (1), Se (2)]. Treatment of 1 with KN(R2PS)2 afforded trans-[Ru(NS)Cl{N(R2PS)2}2] [R = Ph (3), Pr(i) (4), Bu(t) (5)]. Alternatively, the thionitrosyl complex 5 was obtained from [Bu(n)4N][Ru(N)Cl4] and KN(Bu(t)2PS)2, presumably via sulfur atom transfer from [N(Bu(t)2PS)2](-) to the nitride. Reactions of 1 and 2 with NaLOEt (LOEt(-) = [Co(η(5)-C5H5){P(O)(LOEt)2}3](-)) gave [Ru(NX)LOEtCl2] (X = S (8), Se (9)). Treatment of [Bu(n)4N][Ru(N)Cl4] with KN(R2PS)2 produced Ru(IV)-Ru(IV)μ-nitrido complexes [Ru2(μ-N){N(R2PS)2}4Cl] [R = Ph (6), Pr(i) (7)]. Reactions of 3 and 9 with PPh3 afforded 6 and [Ru(NPPh3)LOEtCl2], respectively. The desulfurisation of 5 with [Ni(cod)2] (cod = 1,5-cyclooctadiene) gave the mixed valance Ru(III)-Ru(IV)μ-nitrido complex [Ru2(μ-N){N(Bu(t)2PS)2}4] (10) that was oxidised by [Cp2Fe](PF6) to give the Ru(IV)-Ru(IV) complex [Ru2(μ-N){N(Bu(t)2PS)2}4](PF6) ([10]PF6). The crystal structures of 1, 2, 3, 7, 9 and 10 have been determined.

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“…In contrast, the nonterminal V−N bond length is significantly longer, ∼2.11 Å, as has been shown in [VOC1 2 -(CH 3 CN)(Hpycan)]. 89 The vanadium−nitrogen bond length in the four-coordinated thionitrosyl complex of vanadium [(nacnac)V(NS)(OAr)] is ∼1.68 Å, 90 which clearly indicates that the V−N bond is not a bona fide triple bond but is instead either a double bond or has a partial triple bond character. When the donor nitrogen atom is coordinated to the vanadium center, it results in a single V−N bond with the bond length around 2.11 Å.…”

Section: ■ Experiments and Methodsmentioning

confidence: 81%

NMR Crystallography for Structural Characterization of Oxovanadium(V) Complexes: Deriving Coordination Geometry and Detecting Weakly Coordinated Ligands at Atomic Resolution in the Solid State

Yehl

Hou

et al. 2015

Inorg. Chem.

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NMR crystallography is an emerging method for atomic-resolution structural analysis of ubiquitous vanadium(V) sites in inorganic and bioinorganic complexes as well as vanadium-containing proteins. NMR crystallography allows for characterization of vanadium(V) containing solids, based on the simultaneous measurement of (51)V-(15)N internuclear distances and anisotropic spin interactions, described by (13)C, (15)N, and (51)V chemical shift anisotropy and (51)V electric field gradient tensors. We show that the experimental (51)V, (13)C, and (15)N NMR parameters are essential for inferring correct coordination numbers and deriving correct geometries in density functional theory (DFT) calculations, particularly in the absence of single-crystal X-ray structures. We first validate this approach on a structurally known vanadium(V) complex, ((15)N-salicylideneglycinate)-(benzhydroxamate)oxovanadium(V), VO(15)NGlySalbz. We then apply this approach to derive the three-dimensional structure of (methoxo)((15)N-salicylidene-glycinato)oxovanadium(V) with solvated methanol, [VO((15)NGlySal)(OCH3)]·(CH3OH). This is a representative complex with potentially variable coordination geometry depending on the solvation level of the solid. The solid material containing molecules of CH3OH, formally expressed as [VO((15)NGlySal)(OCH3)]·(CH3OH), is found to have one molecule of CH3OH weakly coordinated to the vanadium. The material is therefore best described as [VO((15)NGlySal)(OCH3)(CH3OH)] as deduced by the combination of multinuclear solid-state NMR experiments and DFT calculations. The approach reported here can be used for structural analysis of systems that are not amenable to single-crystal X-ray diffraction characterization and which can contain weakly associated solvents.

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A four-coordinate thionitrosyl complex of vanadium

Cited by 16 publications

References 29 publications

Mesoionic Carbenes in Low- to High-Valent Vanadium Chemistry

Mesoionic Carbenes in Low- to High-Valent Vanadium Chemistry

Ruthenium chalcogenonitrosyl and bridged nitrido complexes containing chelating sulfur and oxygen ligands

NMR Crystallography for Structural Characterization of Oxovanadium(V) Complexes: Deriving Coordination Geometry and Detecting Weakly Coordinated Ligands at Atomic Resolution in the Solid State

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