Proton-Coupled Electron Transfer from Sulfur: A S-H/S-D Kinetic Isotope Effect of ≥31.1

Huynh, My-Hang V.; White, Peter S.; Meyer, Thomas J.

doi:10.1002/1521-3773(20001117)39:22<4101::aid-anie4101>3.0.co;2-e

Cited by 51 publications

(51 citation statements)

References 32 publications

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“…One-electron reduction of (Tp)Os(Cl) 2 N, 6, in acidic conditions produces the Os(V)-imido species (Tp)Os(Cl) 2 NH. [180] This compound, which is presumably paramagnetic, has an Os=N distance of 1.75 Å , shorter than in the Os(IV) case due to additional Os = N p interactions that can take place. Compound 6 also undergoes a reaction with phenyl-magnesium bromide producing the postulated Os(VI) species [(Tp)Os(Cl) 2 NPh] -, though, due to its rapid reaction with water, the complex was not isolated and characterized.…”

Section: J F Berrymentioning

confidence: 99%

Terminal Nitrido and Imido Complexes of the Late Transition Metals

Berry

2009

Comments on Inorganic Chemistry

285

232

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Compounds that contain a late transition metal-nitrogen multiple bond represent important reactive intermediate species in many useful organic and inorganic transformations. In order to understand the role that these intermediates play in reactions, it is important to have a full understanding of their electronic structure. This paper reviews the known structural motifs that occur in late transition metal nitrido and imido compounds, and provides a correlation between geometric structure and electronic structure. Also, intermediate species that have been postulated but not yet isolated are discussed, as these compounds represent exciting targets for further efforts in synthetic inorganic chemistry.

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Section: J F Berrymentioning

confidence: 99%

Terminal Nitrido and Imido Complexes of the Late Transition Metals

Berry

2009

Comments on Inorganic Chemistry

285

232

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“…When cis-or trans- [Os IV 17 There is also little literature precedence for the coordination of sulfoximido ligands, NS(O)R 2 2-. 18,19 In the structure of [4A] + , the average angle of 109.035 (18) These results are important in demonstrating new routes for the preparation of complexes containing the sulfilimido and sulfoximido ligands, the existence of a multiple-electron-transfer chemistry for the Os-sulfilimido complexes based on the metal, and the existence of a reversible O-atom-transfer reactivity based on the ligand.…”

mentioning

confidence: 99%

Formation and O-Atom Reactivity of the Os(IV)−Sulfilimido and Os(IV)−Sulfoximido Complexes, cis-/trans-[Os^IV(tpy)(Cl)₂(NSC₆H₃Me₂)] and cis-/trans-[Os^IV(tpy)(Cl)₂(NS(O)C₆H₃Me₂)]

2001

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The redox reactions of transition metal-containing sulfoxides and other organosulfur compounds are important both mechanistically and from biochemical and environmental perspectives. 1,2 We recently reported the existence of S-based, proton-coupled electron transfer for the couple trans-[Os V (tpy)(Cl) 2 (NSC 6 H 3 Me 2 )] + /trans-[Os IV (tpy)(Cl) 2 (NS(H)C 6 H 3 Me 2 )] + . 3 We describe here an extension of the known reactivity chemistry of the Os(VI)-nitrido (Os VI tN + ) complexes, cis-/trans-[Os VI (tpy)(Cl) 2 (N)] + , toward bases to give the corresponding sulfilimido complexes. The products, cis-/trans-[Os IV (tpy)(Cl) 2 (NSC 6 H 3 Me 2 )], which are relatively rare examples of sulfilimide coordination, undergo O 2 or air oxidation to give the sulfoximido complexes, cis-/trans-[Os IV -(tpy)(Cl) 2 (NS(O)C 6 H 3 Me 2 )], for which there is also little literature precedence. Remarkably, given the continuing interest in metalcatalyzed oxygen atom transfer in chemistry and biology, the sulfoximido complexes undergo facile, ligand-based O-atom transfer. 4,5 Rapid reactions occur between cis-or trans-[Os VI (tpy)(Cl) 2 -(N)] + and 3,5-Me 2 C 6 H 3 SH in CH 3 CN under Ar at room temperature as indicated by color changes from magenta-purple to reddish brown for the trans isomer and from yellowish brown to reddish maroon for the cis isomer, eq 1.

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“…36 This is in contrast to the reaction of trans-or cis-[Os VI (N)(terpy)Cl 2 ] þ with RSH, which produces the corresponding osmium(IV) sulfilimido species, trans-or cis-[Os VI (NS{H}R)(terpy)Cl 2 ] þ (R = Ph, 4-MePh, or 3,5-Me 2 Ph), where the S atom is protonated instead of the N atom. 12 Moreover, although [Os VI (NS{H}R)(terpy)Cl 2 ] þ is relatively inert, [Ru IV (N{H}SR)(salchda)(NCCH 3 )] þ is able to abstract a H-atom from another thiol or from hydrocarbons with relatively weak CÀH bonds, as shown in Scheme 6.…”

Section: Reaction With Thiols Reaction Of [Ru VI (N)(salchda)-(ch 3 mentioning

confidence: 99%

Reactivity of Nitrido Complexes of Ruthenium(VI), Osmium(VI), and Manganese(V) Bearing Schiff Base and Simple Anionic Ligands

2013

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Nitrido complexes (M≡N) may be key intermediates in chemical and biological nitrogen fixation and serve as useful reagents for nitrogenation of organic compounds. Osmium(VI) nitrido complexes bearing 2,2':6',2″-terpyridine (terpy), 2,2'-bipyridine (bpy), or hydrotris(1-pyrazolyl)borate anion (Tp) ligands are highly electrophilic: they can react with a variety of nucleophiles to generate novel osmium(IV)/(V) complexes. This Account describes our recent results studying the reactivity of nitridocomplexes of ruthenium(VI), osmium(VI), and manganese(V) that bear Schiff bases and other simple anionic ligands. We demonstrate that these nitrido complexes exhibit rich chemical reactivity. They react with various nucleophiles, activate C-H bonds, undergo N···N coupling, catalyze the oxidation of organic compounds, and show anticancer activities. Ruthenium(VI) nitrido complexes bearing Schiff base ligands, such as [Ru(VI)(N)(salchda)(CH3OH)](+) (salchda = N,N'-bis(salicylidene)o-cyclohexyldiamine dianion), are highly electrophilic. This complex reacts readily at ambient conditions with a variety of nucleophiles at rates that are much faster than similar reactions using Os(VI)≡N. This complex also carries out unique reactions, including the direct aziridination of alkenes, C-H bond activation of alkanes and C-N bond cleavage of anilines. The addition of ligands such as pyridine can enhance the reactivity of [Ru(VI)(N)(salchda)(CH3OH)](+). Therefore researchers can tune the reactivity of Ru≡N by adding a ligand L trans to nitride: L-Ru≡N. Moreover, the addition of various nucleophiles (Nu) to Ru(VI)≡N initially generate the ruthenium(IV) imido species Ru(IV)-N(Nu), a new class of hydrogen-atom transfer (HAT) reagents. Nucleophiles also readily add to coordinated Schiff base ligands in Os(VI)≡N and Ru(VI)≡N complexes. These additions are often stereospecific, suggesting that the nitrido ligand has a directing effect on the incoming nucleophile. M≡N is also a potential platform for the design of new oxidation catalysts. For example, [Os(VI)(N)Cl4](-) catalyzes the oxidation of alkanes by a variety of oxidants, and the addition of Lewis acids greatly accelerates these reactions. [Mn(V)(N)(CN)4]2(-) is another highly efficient oxidation catalyst, which facilitates the epoxidation of alkenes and the oxidation of alcohols to carbonyl compounds using H2O2. Finally, M≡N can potentially bind to and exert various effects on biomolecules. For example, a number of Os(VI)≡N complexes exhibit novel anticancer properties, which may be related to their ability to bind to DNA or other biomolecules.

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Proton-Coupled Electron Transfer from Sulfur: A S-H/S-D Kinetic Isotope Effect of ≥31.1

Cited by 51 publications

References 32 publications

Terminal Nitrido and Imido Complexes of the Late Transition Metals

Terminal Nitrido and Imido Complexes of the Late Transition Metals

Formation and O-Atom Reactivity of the Os(IV)−Sulfilimido and Os(IV)−Sulfoximido Complexes, cis-/trans-[Os^IV(tpy)(Cl)₂(NSC₆H₃Me₂)] and cis-/trans-[Os^IV(tpy)(Cl)₂(NS(O)C₆H₃Me₂)]

Reactivity of Nitrido Complexes of Ruthenium(VI), Osmium(VI), and Manganese(V) Bearing Schiff Base and Simple Anionic Ligands

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Proton-Coupled Electron Transfer from Sulfur: A S-H/S-D Kinetic Isotope Effect of ≥31.1

Cited by 51 publications

References 32 publications

Terminal Nitrido and Imido Complexes of the Late Transition Metals

Terminal Nitrido and Imido Complexes of the Late Transition Metals

Formation and O-Atom Reactivity of the Os(IV)−Sulfilimido and Os(IV)−Sulfoximido Complexes, cis-/trans-[OsIV(tpy)(Cl)2(NSC6H3Me2)] and cis-/trans-[OsIV(tpy)(Cl)2(NS(O)C6H3Me2)]

Reactivity of Nitrido Complexes of Ruthenium(VI), Osmium(VI), and Manganese(V) Bearing Schiff Base and Simple Anionic Ligands

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Formation and O-Atom Reactivity of the Os(IV)−Sulfilimido and Os(IV)−Sulfoximido Complexes, cis-/trans-[Os^IV(tpy)(Cl)₂(NSC₆H₃Me₂)] and cis-/trans-[Os^IV(tpy)(Cl)₂(NS(O)C₆H₃Me₂)]