Carbon–Sulfur Bond Formation between a Ruthenium‐Coordinated Thiyl Radical and Methyl Ketones

Poturovic, Selma; Mashuta, Mark S.; Grapperhaus, Craig A.

doi:10.1002/ange.200462713

Cited by 6 publications

(6 citation statements)

References 24 publications

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“…The {Ru‐(SR) 3 } 12 and {Ru‐(SR) 3 } 11 complexes were analyzed as a singlet ( S =0) and doublet ( S =1/2), consistent with experiment 18. 19 The reactive intermediate, {Ru‐(SR) 3 } 10 , possesses a nearly degenerate electronic ground state with respect to frontier orbitals. Consequently, its electronic structure was considered as a singlet diradical, which is consistent with experimental data.…”

Section: Methodsmentioning

confidence: 57%

“…When {Ru‐(SR) 3 } 10 is generated in the presence of methyl ketones, CS bond formation occurs 19. The reaction is presumed to involve the enol tautomer; S‐based reactivity of oxidized Ru thiolates with alkenes was reported by Goh, Webster, and co‐workers 22.…”

Section: Methodsmentioning

confidence: 94%

“…The spectroscopically observable thiyl‐radical intermediate [Ru(dppbt) 3 ] + (dppbt=2‐diphenylphosphinothiaphenolate) displays sulfur‐centered reactivity (Scheme ) and is ideal for DFT investigations 18. 19…”

Section: Methodsmentioning

confidence: 99%

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Singlet Diradical Character of an Oxidized Ruthenium Trithiolate: Electronic Structure and Reactivity

Grapperhaus¹,

Kozłowski²,

Kumar³

et al. 2007

Angew Chem Int Ed

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All alone: The ground state of the oxidized, reactive intermediate [Ru(dppbt)3]+ (dppbt=2‐diphenylphosphinothiaphenolate) is calculated to be a singlet diradical. The unpaired electrons in the π* orbitals are delocalized over the metal atom and the ligand sulfur atoms. The relative orientation of the half‐occupied orbitals inhibits disulfide formation and favors addition of unsaturated hydrocarbons across adjacent sulfur atoms.

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Section: Methodsmentioning

confidence: 57%

Section: Methodsmentioning

confidence: 94%

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Singlet Diradical Character of an Oxidized Ruthenium Trithiolate: Electronic Structure and Reactivity

Grapperhaus¹,

Kozłowski²,

Kumar³

et al. 2007

Angew Chem Int Ed

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“…We note that Grapperhaus lately reported a similar carbon-sulfur bond formation between a Ru(III) thiyl radical and the enol tautomer of acetone. 30 In the absence of AN, IIB dimerizes to form IIIA. A repeat intramolecular electron arrangement then gives the Ru(II)-Ru(II) diradical IIIB, which undergoes a second S-S coupling to give species 63.…”

Section: Electrophilic Reactionsmentioning

confidence: 99%

Pentamethylcyclopentadienyl Ruthenium(III) vs Hexamethylbenzene Ruthenium(II) in Sulfur-Centered Reactivity of Their Thioether-Thiolate and Allied Complexes

Shin

Goh

2006

Acc. Chem. Res.

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The reactivity features of [Cp*Ru(III){eta(3)-tpdt)}] (7) and [(HMB)Ru(II)(eta(3)-tpdt)] (10) {Cp* = eta(5)-C(5)Me(5); HMB = eta(6)-C(6)Me(6); tpdt = 3-thiapentane-1,5-dithiolate, S(CH(2)CH(2)S(-))(2)} are presented, together with selected aspects of their (eta(3)-apdt) analogues 8 and 11 {apdt = 3-azapentane-1,5-dithiolate, HN(CH(2)CH(2)S(-))(2)}. This account will highlight the differences observed in their reactions with metal fragments of compounds of Ru and groups 10 and 11 in various coordination environments and with alkylating agents, including alpha,omega-dibromoalkanes. The mechanistic pathway of the alkylation of 7 will be discussed in some detail.

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“…In contrast, the second class comprises systems that adopt an energetically distinct electronic ground state with a defined spin multiplicity. Reported examples include complexes of radical-anionic dithiolene/dithiophenol ligands shown in Chart 2, part I, 10 radical-salen complexes of palladium 43 (Chart 2, part IV), and octahedral thiyl-radical complexes of ruthenium 33,34 and rhenium 35,36 from 2-phosphinothiophenol (Chart 2, part III). Special cases are complexes that support light-induced ligandto-ligand or metal-to-ligand charge transfer (CT).…”

Section: ■ Introductionmentioning

confidence: 99%

Tuning of Thiyl/Thiolate Complex Near-Infrared Chromophores of Platinum through Geometrical Constraints

et al. 2018

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The chemistry of radical-ligand complexes of the transition metals has developed into a vibrant field of research that spans from fundamental studies on the relationship between the chemical and electronic structures to applications in catalysis and functional materials chemistry. In general, fine-tuning of the relevant properties relies on an increasingly diversifying pool of radical-proligand structures. Surprisingly, the variability of the conformational freedom and the number of distinct bonding modes supported by many radical proligands is limited. This work reports on the angular constraints and relative geometric alignment of metal and ligand orbitals as key parameters that render a series of chemically similar thiyl/thiolate complexes of platinum(II) electronically and spectroscopically distinct. The use of conformational flexible thiophenols as primary ligand scaffolds is essential to establishing a defined radical-ligand [(S)Pt] core whose electronic structure is modulated by a series of auxiliary coligands at platinum.

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Carbon–Sulfur Bond Formation between a Ruthenium‐Coordinated Thiyl Radical and Methyl Ketones

Cited by 6 publications

References 24 publications

Singlet Diradical Character of an Oxidized Ruthenium Trithiolate: Electronic Structure and Reactivity

Singlet Diradical Character of an Oxidized Ruthenium Trithiolate: Electronic Structure and Reactivity

Pentamethylcyclopentadienyl Ruthenium(III) vs Hexamethylbenzene Ruthenium(II) in Sulfur-Centered Reactivity of Their Thioether-Thiolate and Allied Complexes

Tuning of Thiyl/Thiolate Complex Near-Infrared Chromophores of Platinum through Geometrical Constraints

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