The reactions of triethylamine-activated octasulfur with thioarsinites, L2As‒SPh (L = Me, Ph), Bunsen's cacodyl disulfide, Me2As(S)‒S‒AsMe2, and triphenylarsine

Sideris, Theodore D.; Tsivgoulis, Gerasimos M.; Vachliotis, Dimitris G.; Ioannou, Panayiotis V.

doi:10.1080/10241220903134429

Cited by 3 publications

(2 citation statements)

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“…Triphenylarsine did not react at all with 2 in CDCl 3 , as the sharp singlet signal at δ = 7.34 ppm in the 1 H NMR spectrum revealed, whereas the 31 P NMR spectrum after 3 d at room temperature showed 2 , traces of 3 , and four unknown species. Triphenylarsine sulfide, Ph 3 As=S, is difficult to prepare, and its 1 H NMR spectrum, now recorded, in CDCl 3 showed multiplets at δ = 7.50 and 7.74 ppm.…”

Section: Resultsmentioning

confidence: 97%

The Reaction of Diethylthiophosphinyl Iodide, Et₂P(S)I, with Nucleophiles

Tsivgoulis

Kordopati

Vachliotis

et al. 2017

Zeitschrift anorg allge chemie

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The compound Me 2 AsSI can exist in two different forms, either as dimethylarsinosulfenyl iodide [or (iodothio)dimethylarsane)], Me 2 As-S-I (A), or as dimethylthioarsinyl iodide (or dimethylarsinothioic iodide), Me 2 As(S)-I (B). To confirm that the structure of the product of the reaction between Bunsen's cacodyl disulfide Me 2 As(S)-S-AsMe 2 and iodine is A and not B, the known diethylthiophosphinyl iodide (or diethylphosphinothioic iodide), Et 2 P(S)-I (2) was prepared and its hydrolytic stability and reactivity towards a variety of nitrogen, phosphorus(III), arsenic(III), oxygen, and sulfur(II) nucleophiles were * Associate Prof. Dr. G. M. Tsivgoulis Fax: +30-2610997118 E-Mail: tsivgoulis@chemistry.upatras.gr [a]

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Section: Resultsmentioning

confidence: 97%

The Reaction of Diethylthiophosphinyl Iodide, Et₂P(S)I, with Nucleophiles

Tsivgoulis

Kordopati

Vachliotis

et al. 2017

Zeitschrift anorg allge chemie

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“…Bubbling H 2 S for 5 min to a solution of 1 + 2 very slowly (12 days) resulted in the disappearance of 2 but the reaction was not studied further 5. With a strong nucleophile, triethylamine‐activated octasulfur, 1 reacted slowly reaching an equilibrium containing 1 and the ions Me 2 As‐S‐NEt 3 + and Me 2 As(S)‐S – 14. With an even stronger nucleophile, S 2– + 1/8S 8 , the disulfide 1 gave the salt Me 2 AsS 2 Na · 2H 2 O ( 3b ) 9,11…”

Section: Introductionmentioning

confidence: 99%

The Electrophilic Character of Bunsen's Cacodyl Disulfide, Me₂As(S)‐S‐AsMe₂, Towards Some Nucleophiles of Groups 15 and 16

Ioannou

Vachliotis

2015

Zeitschrift anorg allge chemie

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The reactivity of Bunsen's cacodyl disulfide, Me 2 As(S)-S-AsMe 2 , towards nitrogen, phosphorus(III), oxygen and sulfur(II) nucleophiles was evaluated with the aim at identifying its electrophilic atom. The nitrogen nucleophiles either did not react or bind or split the disulfide. All phosphorus(III) nucleophiles desulfurized it. Water, methanol and phenol did not react but thiophenol reacted IntroductionThe great experimental chemist Robert Bunsen [1] in 1843 prepared a compound Me 4 As 2 S 2 which he named cacodyl disulfide by reducing cacodylic acid, Me 2 AsO 2 H, with hydrogen sulfide. [2] Its structure was not the expected As III /As III bis(dimethylarsenic)disulfide (2) but the As V /As III dimethylarsino dimethyldithioarsinate [3,4 ] and mechanisms of its formation have been proposed. [4,5] Bunsen's cacodyl disulfide (1) is a remarkable chemical chameleon. When dissolved in non-basic solvents it equilibrates with 2 to the extent of approx. 10 %, thus showing an internal redox property. [6] Bunsen, apart from studying the behavior of his disulfide towards heat, HCl, H 2 SO 4 and HNO 3 , he found that it reacted with metal salts of the non-reducible metals Pb II , Sb III and Bi III giving the complexes (Me 2 AsS 2 ) x M (= L x M) [2] and we extended the list by preparing complexes with Zn II , Cd II and Ag I under conditions that afforded pure products. [7] With compounds of lighter metals like AlCl 3 , compound 1 was isomerized to 2, GaCl 3 and InCl 3 bound to 1, while Tl(AcO) 3 was reduced giving LTl. [8] Bunsen himself also found that the reducible Au III and Cu II gave the complexes LAu and LCu [2] and we [7] verified the production of LCu identifying some by-products. Pd II also produced L 2 Pd that was unstable and decomposed to unknown compounds, [9] but Hg II was not reduced. [7] It was proposed [7,8] that the electron for the reduction came from the bound Me 2 AsS 2 group and reasonable

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Trithioarsenites [(RS)3As], dithioarsonites [R-As(SR′)2] and thioarsinites [R2As-SR′]: Preparations, chemical, biochemical and biological properties

Ioannou

2022

MGC

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Contrary to P(V) compounds, As(V) compounds can very easily reduced by thiols to As(III) thiolates that are deemed to play a central role in the metabolism of arsenic and therefore a review on the preparation and properties of the title thiolates can be of interest. The preparation of trithioarsenites, dithioarsonites and thioarsinites involves reactions of a thiol with a proper As(V) or As(III) precursor via 4-centered transition states or a thiolate by SN2 mechanisms. Convenient precursors are the solids As2O3, arsonic and arsinic acids, although for the latter two acids the separation of the product from the co-produced disulfides can be problematic. Only a few crystal structures have been reported and involve only trithioarsenites. From their chemical properties, the hydrolyses, transthiolations and air oxidations are of particular interest from mechanistic and biochemical/biological points of view. Their nucleophilicity towards alkyl halides and acyl derivatives revealed unexpected behavior. Although these molecules have many free electron pairs only three reports were found pertaining to their reaction with metal cations (Hg2+) and metal carbonyls; the mercuric complexes being not characterized. Only a few studies appeared for the action of the title compounds towards enzymes, while the patent literature revealed that they have bactericidal, fungicidal and insecticidal activities for agricultural applications, some have antiparasitic activity on animals and a few are carcinostatic.

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The reactions of triethylamine-activated octasulfur with thioarsinites, L₂As‒SPh (L = Me, Ph), Bunsen's cacodyl disulfide, Me₂As(S)‒S‒AsMe₂, and triphenylarsine

Cited by 3 publications

References 34 publications

The Reaction of Diethylthiophosphinyl Iodide, Et₂P(S)I, with Nucleophiles

The Reaction of Diethylthiophosphinyl Iodide, Et₂P(S)I, with Nucleophiles

The Electrophilic Character of Bunsen's Cacodyl Disulfide, Me₂As(S)‐S‐AsMe₂, Towards Some Nucleophiles of Groups 15 and 16

Trithioarsenites [(RS)3As], dithioarsonites [R-As(SR′)2] and thioarsinites [R2As-SR′]: Preparations, chemical, biochemical and biological properties

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The reactions of triethylamine-activated octasulfur with thioarsinites, L2As‒SPh (L = Me, Ph), Bunsen's cacodyl disulfide, Me2As(S)‒S‒AsMe2, and triphenylarsine

Cited by 3 publications

References 34 publications

The Reaction of Diethylthiophosphinyl Iodide, Et2P(S)I, with Nucleophiles

The Reaction of Diethylthiophosphinyl Iodide, Et2P(S)I, with Nucleophiles

The Electrophilic Character of Bunsen's Cacodyl Disulfide, Me2As(S)‐S‐AsMe2, Towards Some Nucleophiles of Groups 15 and 16

Trithioarsenites [(RS)3As], dithioarsonites [R-As(SR′)2] and thioarsinites [R2As-SR′]: Preparations, chemical, biochemical and biological properties

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The reactions of triethylamine-activated octasulfur with thioarsinites, L₂As‒SPh (L = Me, Ph), Bunsen's cacodyl disulfide, Me₂As(S)‒S‒AsMe₂, and triphenylarsine

The Reaction of Diethylthiophosphinyl Iodide, Et₂P(S)I, with Nucleophiles

The Reaction of Diethylthiophosphinyl Iodide, Et₂P(S)I, with Nucleophiles

The Electrophilic Character of Bunsen's Cacodyl Disulfide, Me₂As(S)‐S‐AsMe₂, Towards Some Nucleophiles of Groups 15 and 16