Synthesis and Characterization of Osmium Nitrosyl Porphyrins Containing Organo, Halogeno, and μ-Oxo Ligands, and Extensions to the First Organometallic Thionitrosyl Porphyrin

Cheng, Lin; Chen, Li; Chung, Hee Soon; Khan, Masood A.; Richter‐Addo, George B.; Young, Victor G.

doi:10.1021/om980197s

Cited by 27 publications

(20 citation statements)

References 90 publications

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“…The sulfidation of transition metal nitrides with elemental sulfur to give thionitrosyl complexes has been reported. 2,[10][11][12]14,19 Also, metal-mediated desulfurisation of dithioimidodiphosphinate ligands is well precedented. 33,34 μ-Nitrido complexes and dinitrogen.…”

Section: Thionitrosyl Complexesmentioning

confidence: 99%

“…While nitrosyl complexes of transition metals are well documented, 1 the chemistry of 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 in 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%

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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: Thionitrosyl Complexesmentioning

confidence: 99%

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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“…8 Other neutral (por)Os(NO)X compounds (X = halide, 9 alkoxide, 10, 11 thiolate, 11, 12 ONO, 13 OClO 3 , 14 O 2 PF 2 , 11 alkyl/aryl 9 ) have since been described, including the l-oxo dimer [(OEP)Os(NO)] 2 (l-O). 9 Several related ruthenium compounds (por)Ru(NO)X (X = halide, O-donor, S-donor, N-donor, Cdonor) have also been reported. [14][15][16][17][18][19][20][21][22][23][24][25][26][27][28][29][30] As part of our studies on the class of Os and Ru nitrosyl porphyrins containing alkoxide and thiolate trans ligands, we investigated the redox behavior of a representitive set of these species.…”

Section: Introductionmentioning

confidence: 99%

Fiber-optic infrared reflectance spectroelectrochemical studies of osmium and ruthenium nitrosyl porphyrins containing alkoxide and thiolate ligands

et al. 2006

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We have examined the redox behavior of the osmium and ruthenium compounds (OEP)M(NO)(OEt) and (OEP)M(NO)(SEt) (OEP = octaethylporphyrinato dianion; M = Os, Ru) by cyclic voltammetry and infrared spectroelectrochemistry. The compound (OEP)Os(NO)(OEt) undergoes a single reversible oxidation process in dichloromethane. In contrast, the thiolate compound (OEP)Os(NO)(SEt) undergoes a net irreversible oxidation resulting in formal loss of the SEt ligand. Extended Hückel calculations on crystal structures of these two compounds provide insight into the nature of their HOMOs. In the case of the alkoxide compound, the HOMO is largely metal centered, with 70% of the charge located in the metal's orbital and approximately 25% on the porphyrin ring. However, the HOMO of the thiolate compound consists of a pi bonding interaction between the metal dxz orbital and the px orbital on the sulfur, and a pi antibonding interaction between the metal d orbital and a pi* orbital on NO. The redox behavior of the Ru analogues have been determined, and are compared with those of the Os compounds.

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“…Some of these structures have demonstrated the ability to release nitric oxide under visible light, making them possibly useful candidates for nitric oxide transfer reactions [114–117]. Other structures make use of porphyrins as a bulky ligand in order to stabilize the nitric oxide group, and an axially bound NO on cobalt porphyrins with the formula (T( p / m -X)PP)Co(NO) ( p / m -X = p -OCH 3 , p -CH 3 , m -CH 3 , p -H, m -OCH 3 , p -OCF 3 , p -CF 3 , p -CN) [118, 119], and with a ruthenium metal [120, 121]. Photoliability studies on mixed-type structures with both S and N ligands were also examined [122, 123].…”

Section: Mononitrosyl and Trinitrosyl Complexesmentioning

confidence: 99%

The Preparation, Structural Characteristics, and Physical Chemical Properties of Metal-Nitrosyl Complexes

Holloway

2013

Nitrosyl Complexes in Inorganic Chemistry, Biochemistry and Medicine II

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The preparation and characterization of a representative group of novel non-heme metal nitrosyl complexes that have been synthesized over the last decade are discussed here. Their structures are examined and classified based on metal type, the number of metal centers present, and the type of ligand that is coordinated with the metal. The ligands can be phosphorus, nitrogen, or sulfur based (with a few exceptions) and can vary depending on the presence of chelation, intermolecular forces, or the presence of other ligands. Structural and bonding characteristics are summarized and examples of reactivity regarding nitrosyl ligands are given. Some of the relevant physical chemical properties of these complexes, including IR, EPR, NMR, UV–vis, cyclic voltammetry, and X-ray crystallography are examined.

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Synthesis and Characterization of Osmium Nitrosyl Porphyrins Containing Organo, Halogeno, and μ-Oxo Ligands, and Extensions to the First Organometallic Thionitrosyl Porphyrin

Abstract: Figure 6. Molecular structure of (OEP)Os(NS)Me. Only one of the two disordered axial SN-Os-Me orientations is shown.

Cited by 27 publications

References 90 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

Fiber-optic infrared reflectance spectroelectrochemical studies of osmium and ruthenium nitrosyl porphyrins containing alkoxide and thiolate ligands

The Preparation, Structural Characteristics, and Physical Chemical Properties of Metal-Nitrosyl Complexes

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