The electronic structure and photochemistry of transition metal thionitrosyl complexes

Døssing, Anders

doi:10.1016/j.ccr.2015.02.020

Cited by 9 publications

(1 citation statement)

References 74 publications

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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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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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Construction of a Metal‐Free Electron Spin System by Encapsulation of an NO Molecule Inside an Open‐Cage Fullerene C₆₀ Derivative

et al. 2018

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A reactive radical species, nitric oxide (NO), was encapsulated in a unimolecular form inside an open‐cage fullerene derivative under high‐pressure conditions in the solid state. Surprisingly, the molecular complex showed sharp 1H NMR signals despite the existence of the paramagnetic species inside the carbon cage. Owing to the paramagnetic shifts, the escape rate of the NO was determined experimentally. After constructing a stopper on the rim of the opening, the NO was found to stay inside the cage even at 50 °C. The ESR measurements of the powdery sample showed paramagnetic properties at low temperature. The single‐crystal X‐ray structure analysis clearly demonstrated the existence of the encapsulated NO molecule, suggesting rapid rotation inside the cage. The 1H NMR chemical shifts displayed a large temperature dependence owing to the paramagnetic effects.

show abstract

Construction of a Metal‐Free Electron Spin System by Encapsulation of an NO Molecule Inside an Open‐Cage Fullerene C₆₀ Derivative

et al. 2018

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A reactive radical species, nitric oxide (NO), was encapsulated in a unimolecular form inside an open-cage fullerene derivative under high-pressure conditions in the solid state. Surprisingly, the molecular complex showed sharp H NMR signals despite the existence of the paramagnetic species inside the carbon cage. Owing to the paramagnetic shifts, the escape rate of the NO was determined experimentally. After constructing a stopper on the rim of the opening, the NO was found to stay inside the cage even at 50 °C. The ESR measurements of the powdery sample showed paramagnetic properties at low temperature. The single-crystal X-ray structure analysis clearly demonstrated the existence of the encapsulated NO molecule, suggesting rapid rotation inside the cage. The H NMR chemical shifts displayed a large temperature dependence owing to the paramagnetic effects.

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The electronic structure and photochemistry of transition metal thionitrosyl complexes

Cited by 9 publications

References 74 publications

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

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

Construction of a Metal‐Free Electron Spin System by Encapsulation of an NO Molecule Inside an Open‐Cage Fullerene C₆₀ Derivative

Construction of a Metal‐Free Electron Spin System by Encapsulation of an NO Molecule Inside an Open‐Cage Fullerene C₆₀ Derivative

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The electronic structure and photochemistry of transition metal thionitrosyl complexes

Cited by 9 publications

References 74 publications

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

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

Construction of a Metal‐Free Electron Spin System by Encapsulation of an NO Molecule Inside an Open‐Cage Fullerene C60 Derivative

Construction of a Metal‐Free Electron Spin System by Encapsulation of an NO Molecule Inside an Open‐Cage Fullerene C60 Derivative

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Construction of a Metal‐Free Electron Spin System by Encapsulation of an NO Molecule Inside an Open‐Cage Fullerene C₆₀ Derivative

Construction of a Metal‐Free Electron Spin System by Encapsulation of an NO Molecule Inside an Open‐Cage Fullerene C₆₀ Derivative