3111-52-2Relevant articles and documents
Utility of a redox-active pyridine(diimine) chelate in facilitating two electron oxidative addition chemistry at uranium
Kiernicki, John J.,Fanwick, Phillip E.,Bart, Suzanne C.
, p. 8189 - 8192 (2014)
Exposure of the uranium(iv) complex, CpPU(MesPDI Me) (1) (MesPDIMe = 2,6-((Mes)NCMe) 2-C5H3N; Mes = 2,4,6-trimethylphenyl; Cp P = 1-(7,7-dimethylbenzyl)cyclopentadienyl), which contains a [ MesPDIMe]3- chelate, to I2, Cl 2, PhSeCl, and PhEEPh (E = S, Se, Te) results in oxidative addition to form the uranium(iv) family, CpPU(XX′)( MesPDIMe) (X = X′ = I, Cl, EPh; X = SePh, X′ = Cl). Spectroscopic and structural studies support products with [ MesPDIMe]1-, indicating the reducing equivalents derive from this redox-active chelate. This journal is the Partner Organisations 2014.
New approaches to synthesis of unsaturated organochalcogen compounds with two different chalcogen atoms
Levanova,Vakhrina,Grabel'Nykh,Rozentsveig,Russavskaya,Albanov,Sanzheeva,Korchevin
, p. 2130 - 2137 (2014)
Two approaches to synthesis of bis-chalcogenyl derivatives of propene with two different chalcogen atoms are proposed. Reaction of 2,3-dichloro-1-propene with two different chalcogen nucleophiles PhY- (Y = S, Se) results in a mixture of two pro
Inherent Reactivity of Spiro-Activated Electrophilic Cyclopropanes
Jüstel, Patrick M.,Ofial, Armin R.,Pignot, Cedric D.,Stan, Alexandra
supporting information, p. 15928 - 15935 (2021/10/25)
The kinetics of the ring-opening reactions of thiophenolates with geminal bis(acceptor)-substituted cyclopropanes in DMSO at 20 °C was monitored by photometric methods. The determined second-order rate constants of the SN2 reactions followed linear relationships with Mayr nucleophilicity parameters (N/sN) and Br?nsted basicities (pKaH) of the thiophenolates as well as with Hammett substituent parameters (σ) for groups attached to the thiophenolates. Phenyl-substituted cyclopropanes reacted by up to a factor of 15 faster than their unsubstituted analogues, in accord with the known activating effect of adjacent π-systems in SN2 reactions. Variation of the electronic properties of substituents at the phenyl groups of the cyclopropanes gave rise to parabolic Hammett relationships. Thus, the inherent SN2 reactivity of electrophilic cyclopropanes is activated by electron-rich π-systems because of the more advanced C1?C2 bond polarization in the transition state. On the other hand, electron-poor π-systems also lower the energetic barriers for the attack of anionic nucleophiles owing to attractive electrostatic interactions.
Nucleophilic Cleavage of the Ether Bond of Chlorex in the Chalcogenation with Diphenyl Dichalcogenides in the System Hydrazine Hydrate–KOH
Albanov, A. I.,Bogdanova, I. N.,Grabel?nykh, V. A.,Istomina, N. V.,Korchevin, N. A.,Nikonova, V. S.,Rozentsveig, I. B.,Russavskaya, N. V.,Sosnovskaya, N. G.
, p. 1760 - 1762 (2020/10/15)
Abstract: The synthesis of unsymmetrical pincer ligands by reactions of diphenyl disulfide and diphenyl diselenide with bis(2-chloroethyl) ether in the system hydrazine hydrate–KOH was accompanied by the formation of 1,2-bis(phenylsulfanyl)ethane, 1,2-bis(phenylselanyl)ethane, and 1-(phenylselanyl)-2-(phenylsulfanyl)ethane as by-products with an overall yield of 23% as a result of nucleophilic cleavage of the C–O–C bond in the initial ether.
Synthesis and luminescence studies of lanthanide complexes (Gd, Tb, Dy) with phenyl- And 2-pyridylthiolates supported by a bulky β-diketiminate ligand. Impact of the ligand environment on terbium(iii) emission
Mironova, Olga A.,Ryadun, Aleksey A.,Sukhikh, Taisiya S.,Konchenko, Sergey N.,Pushkarevsky, Nikolay A.
, p. 19769 - 19779 (2020/12/05)
The range of lanthanide complexes with bulky N,N′-bis(Dipp)-substituted β-diketiminate ligand Nacnac- = CH(CMe(NDipp))2- (Dipp = 2,6-diisopropylphenyl) has been expanded to the complexes [Ln(Nacnac)I2(thf)n] (1Ln, Ln = Gd, Tb, n = 2; Dy, n = 1; thf = tetrahydrofuran). They were further used in salt metathesis reactions with KSPh and KS(2-Py) (2-Py = 2-pyridyl), resulting in thiolato complexes [Ln(Nacnac)(SPh)2(thf)] (2Ln) and [Ln(Nacnac)(SPy)2] (3Ln). As an analogue of 2Tb without coordinated thf molecules, binuclear complex [{Tb(Nacnac)(SPh)}2(μ-SPh)2] (4Tb) was obtained by reaction of dry TbI3 with K(Nacnac) and KSPh in Et2O followed by recrystallization from toluene. The diiodo complexes possess different numbers of coordinated thf molecules and different coordination polyhedra owing to the lanthanide contraction. On the contrary, all 2Ln and 3Ln have the same molecular and crystal structures for a given thiolate, owing to the coordination rigidity provided by edge coordination of a Ph cycle or by chelating binding of a S(2-Py)- ligand. UV-vis and photoluminescence spectra were registered for all compounds. A triplet level of the Nacnac- ligand of 2.22 × 104 cm-1 was determined from the solid-state emission of Gd complex 1Gd at 77 K; the triplet level in 2Gd and 3Gd was found at 2.16 × 104 cm-1. Emission lifetimes and quantum yields were measured for all Tb compounds with the highest values for thiolato complexes 2Tb and 3Tb, while 1Tb showed only weak emission. The relationship of the emission properties with the molecular and crystal structures is discussed, and better antenna properties are proposed for thiolato rather than for Nacnac- ligands. This journal is
Chalcogenation of 1,3-Dichlorobut-2-ene with Organic Dichalcogenides in the System Hydrazine Hydrate–Alkali
Levanova,Nikonova,Grabel’nykh,Russavskaya,Chirkina,Albanov,Rozentsveig,Korchevin
, p. 1754 - 1759 (2019/03/26)
Electron-donor effect of the methyl group in 1,3-dichlorobut-2-ene hampers allylic rearrangement of its primary monochalcogenation products. The use of diphenyl disulfide under harsh conditions (Ph2S2–KOH, 1: 10, 75–80°C) makes it possible to obtain a mixture of six bis(phenylsulfanyl)butenes, 1,1-bis(phenylsulfanyl) but-1-ene being the major component. No bis(phenylselanyl) derivatives have been formed on heating up to 80°C. Dipotassium ethane-1,2-dithiolate reacts with 1,3-dichlorobut-2-ene to give a linear product of chlorine substitution at the sp3-carbon atom in two dichlorobutene molecules and a heterocyclic compound, 2-ethylidene-1,4-dithiane (a mixture of E and Z isomers), whose structure is different from the structure of the product obtained from 1,3-dichloropropene under analogous conditions. Mechanisms have been proposed for the formation of the isolated compounds.
Synthesis of polydentate chalcogen-containing ligands using the system hydrazine hydrate–base
Levanova,Vilms,Bezborodov,Babenko,Sosnovskaya,Istomina,Albanov,Russavskaya,Rozentsveig
, p. 396 - 401 (2017/05/01)
The reaction of dichlorodiethyl ether or dichlorodiethylamine hydrochloride with potassium or ethanolammonium dichalcogenides prepared in situ from elemental sulfur or selenium in the system hydrazine hydrate–alkali results in oligomeric dichalcogenides,
Effect of chalcogenyl substituent on the course of allyl rearrangement at chalcogenation of 1,3-dichloropropene
Levanova,Nikonova,Grabel’nykh,Russavskaya,Albanov,Rozentsveig,Korchevin
, p. 615 - 623 (2016/07/06)
Formation of 1,3-dichalcogenylpropene at the treatment of 1,3-dichloropropene with organic dichalcogenides in a redox system hydrazine hydrate–KOH is governed by the possibility of an allyl rearrangement. In the presence of bases this rearrangement proceeds via carbanion partially stabilized by the chalcogenyl substituent. The effectivity of the stabilization and consequently the probability of the rearrangement varies in the series of substituents PhS > BnS > PhSe. In the stage of the direct nucleophilic substitution of chlorine the anion PhSe?possesses the highest activity.
Chalcogenation of 1,4-dichlorobut-2-yne with organic dichalcogenides in the system hydrazine hydrate–KOH
Levanova,Vakhrina,Grabel’nykh,Rozentsveig,Russavskaya,Albanov,Klyba,Korchevin
, p. 2083 - 2089 (2016/10/03)
A reaction of organic dichalcogenides R2Y2 (R = Ph, Bn, Pr; Y = S, Se) with 1,4-dichlorobut-2-yne in the system hydrazine hydrate–KOH leads to four principal products: 1,4-bis(organylchalcogenyl)but-2-ynes, 1-organylchalcogenylbut-1-en-3-ynes, 4-organylchalcogenylbut-1-en-3-ynes, and 3(5)-methylpyrazole. The selectivity of the formation of individual products is determined by the ratio of the substrates used and the reaction temperature. A plausible mechanism of chalcogenation considered in the work agrees with the effect of the nature of chalcogene atoms and organic substituents R on stability of intermediates and products. The stabilization of carbanions by α chalcogene-containing groups corresponds to the following order: PhS > PhSe > BnS > BnSe > PrS.
Mechanism and stereochemistry of domino reaction of 2,3-dichloroprop-1-ene with diphenyl dichalcogenides in the system hydrazine hydrate - KOH
Levanova,Vakhrina,Grabel'Nykh,Rozentsveig,Russavskaya,Albanov,Korchevin
, p. 1722 - 1727 (2015/05/20)
A new scheme of the domino reactions of diphenyl dichalcogenides with 2,3-dichloroprop-1-ene in the system hydrazine hydrate - KOH was suggested, which included nucleophilic substitution of the allylic chlorine atom in dichloropropene, dehydrochlorination of the product obtained with the formation of an allene derivative, addition of a nucleophile to the allene system, allene-acetylene rearrangement, addition of a nucleophile to the triple bond with the formation of a Z-adduct, isomerization of a 2,3-dichalcogenide product to Z-1,2-dichalcogenylprop-1-enes, and isomerization of Z-adducts to E-isomers. The most plausible mechanisms of individual steps, involving carbanions stabilized by the α-chalcogen atom, were considered.
