3878-44-2Relevant articles and documents
Mechanism of catalytic chalcogen atom replacement of phosphine chalcogenides and separation of the intermediate phosphine
Aizawa, Sen-Ichi,Majumder, Arpi,Maeda, Daisuke,Kitamura, Akina
, p. 18 - 19 (2009)
The reaction mechanism of the chalcogen atom replacement of phosphine chalcogenides has been revealed to be dissociative from a kinetic investigation for the reaction of phosphine selenide with sulfur. The dissociation is enthalpically promoted by the catalysis of Pd0. For a bidentate phosphine chalcogenide, the intermediate phosphine was separated as the Pd II complex by the catalysis and oxidative addition of Pd0 complex. The novel catalytic replacement and dissociation of chalcogen atom are applicable to regeneration of phosphines from their oxides via the phosphine sulfides. Copyright
Phosphorus-Chalcogen Ring Expansion and Metal Coordination
Graham, Cameron M. E.,Valjus, Juuso,Pritchard, Taylor E.,Boyle, Paul D.,Tuononen, Heikki M.,Ragogna, Paul J.
, p. 13500 - 13509 (2017)
The reactivity of 4-membered (RPCh)2 rings (Ch = S, Se) that contain phosphorus in the +3 oxidation state is reported. These compounds undergo ring expansion to (RPCh)3 with the addition of a Lewis base. The 6-membered rings were found to be more stable than the 4-membered precursors, and the mechanism of their formation was investigated experimentally and by density functional theory calculations. The computational work identified two plausible mechanisms involving a phosphinidene chalcogenide intermediate, either as a free species or stabilized by a suitable base. Both the 4- and 6-membered rings were found to react with coinage metals, giving the same products: (RPCh)3 rings bound to the metal center from the phosphorus atom in tripodal fashion.
Reaction of 1,2,3-selenadiazoles with phosphines
Arsenyan,Oberte,Rubina,Belyakov,Lukevics
, p. 503 - 506 (2004)
Nucleophilic attack of tributyl- and triphenylphosphines on 4-phenyl- and 5-ethoxycarbonyl-4-methyl-1,2,3-selenadiazoles leads to the quantitative formation of selenophosphoranes and substituted acetylenes. The molecular structure of 4-phenyl-1,2,3-selenadiazole was confirmed by X-ray crystallography.
Oxo-sulfido- and oxo-selenido-molybdenum(vi) complexes possessing a dithiolene ligand related to the active sites of hydroxylases of molybdoenzymes: Low temperature preparation and characterisation
Sugimoto, Hideki,Tatemoto, Susumu,Toyota, Kazuo,Ashikari, Kenji,Kubo, Minoru,Ogura, Takashi,Itoh, Shinobu
, p. 4358 - 4360 (2013)
Oxo-sulfido- and oxo-selenido-molybdenum(vi) complexes with an ene-1,2-dithiolate ligand are generated as models of the active sites of molybdenum hydroxylases. The sulfide and selenide groups are highly reactive toward triphenylphosphine in the order of Se > S.
Novel formation of 1,2,4-triselenolanes by the reaction of tert-butylarylmethylenetriphenylphosphoranes with elemental selenium
Okuma, Kentaro,Kubota, Tomoaki
, p. 3881 - 3883 (2001)
Reaction of tert-butylarylmethylenetriphenylphosphoranes with elemental selenium afforded the corresponding 1,2,4-triselenolanes (1), 1,3-diselenetanes (4), and triphenylphosphine selenide. Triselenolanes 1 were formed from selenation of 4, which may suggest a stepwise selenation of selenoketones.
Ruthenium chalcogenonitrosyl and bridged nitrido complexes containing chelating sulfur and oxygen ligands
Ng, Ho-Yuen,Cheung, Wai-Man,Kwan Huang, Enrique,Wong, Kang-Long,Sung, Herman H.-Y.,Williams, Ian D.,Leung, Wa-Hung
, p. 18459 - 18468 (2015)
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), Pri (4), But (5)]. Alternatively, the thionitrosyl complex 5 was obtained from [Bun4N][Ru(N)Cl4] and KN(But2PS)2, presumably via sulfur atom transfer from [N(But2PS)2]- to the nitride. Reactions of 1 and 2 with NaLOEt (LOEt- = [Co(η5-C5H5){P(O)(LOEt)2}3]-) gave [Ru(NX)LOEtCl2] (X = S (8), Se (9)). Treatment of [Bun4N][Ru(N)Cl4] with KN(R2PS)2 produced RuIV-RuIV μ-nitrido complexes [Ru2(μ-N){N(R2PS)2}4Cl] [R = Ph (6), Pri (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 RuIII-RuIV μ-nitrido complex [Ru2(μ-N){N(But2PS)2}4] (10) that was oxidised by [Cp2Fe](PF6) to give the RuIV-RuIV complex [Ru2(μ-N){N(But2PS)2}4](PF6) ([10]PF6). The crystal structures of 1, 2, 3, 7, 9 and 10 have been determined.
Heteroleptic Samarium(III) Chalcogenide Complexes: Opportunities for Giant Exchange Coupling in Bridging σ- And π-Radical Lanthanide Dichalcogenides
Dimucci, Ida M.,Giansiracusa, Marcus J.,Goodwin, Conrad A. P.,Kragskow, Jon G. C.,Lancaster, Kyle M.,Mills, David P.,Réant, Benjamin L. L.,Sproules, Stephen,Vettese, Gianni F.
supporting information, (2020/06/08)
The introduction of (N2)3-? radicals into multinuclear lanthanide molecular magnets raised hysteresis temperatures by stimulating strong exchange coupling between spin centers. Radical ligands with larger donor atoms could promote more efficient magnetic coupling between lanthanides to provide superior magnetic properties. Here, we show that heavy chalcogens (S, Se, Te) are primed to fulfill these criteria. The moderately reducing Sm(II) complex, [Sm(N??)2], where N?? is the bulky bis(triisopropylsilyl)amide ligand, can be oxidized (i) by diphenyldichalcogenides E2Ph2 (E = S, Se, Te) to form the mononuclear series [Sm(N??)2(EPh)] (E = S, 1-S; Se, 1-Se, Te, 1-Te); (ii) S8 or Se8 to give dinuclear [{Sm(N??)2}2(μ-η2:η2-E2)] (E = S, 2-S2; Se, 2-Se2); or (iii) with Te=PEt3 to yield [{Sm(N??)2}(μ-Te)] (3). These complexes have been characterized by single crystal X-ray diffraction, multinuclear NMR, FTIR, and electronic spectroscopy; the steric bulk of N?? dictates the formation of mononuclear complexes with chalcogenate ligands and dinuclear species with the chalcogenides. The Lα1 fluorescence-detected X-ray absorption spectra at the Sm L3-edge yielded resolved pre-edge and white-line peaks for 1-S and 2-E2, which served to calibrate our computational protocol in the successful reproduction of the spectral features. This method was employed to elucidate the ground state electronic structures for proposed oxidized and reduced variants of 2-E2. Reactivity is ligand-based, forming species with bridging superchalcogenide (E2)-? and subchalcogenide (E2)3-? radical ligands. The extraordinarily large exchange couplings provided by these dichalcogenide radicals reveal their suitability as potential successors to the benchmark (N2)3-? complexes in molecular magnets.
Synthesis of Phosphine Chalcogenides Under Solvent-Free Conditions Using a Rotary Ball Mill
Kumar, Rajnish,Kumar, Saurabh,Pandey, Madhusudan K.,Kashid, Vitthalrao S.,Radhakrishna, Latchupatula,Balakrishna, Maravanji S.
, p. 1028 - 1037 (2018/02/26)
The mechanochemical technique of ball milling has been applied to the solventless and eco-friendly synthesis of chalcogenides (sulfide and selenide) of a variety of tertiary and aminophosphines. In most of the cases, the products are obtained in almost quantitative yields with high purity by applying a simple workup procedure without using chromatographic techniques or any other purification methods. The scope of this methodology was explored by using a range of phosphines (mono, di and tetra) to synthesize partial as well as mixed chalcogenides. The use of almost equimolar amounts of starting materials and the absence of any byproducts significantly simplifies the product isolation compared with the standard solution state reactions, thus providing a highly atom economic (100 %) method with an ideal E-factor (E = 0). The solid-state reactions were monitored by 31P{1H} NMR spectroscopy. The structures of some of the products are also confirmed by single-crystal X-ray analyses. Although most of the reactions were carried out on ca. 100-mg scale, the scaling up of the reaction did not affect the course of the reaction.
Assessing the Activity of Lewis Bases Organocatalysts in Halonium-Induced Carbocyclization Reactions
Grandclaudon, Charlotte,Ruamps, Mirko,Duboc, Rapha?l,Michelet, Véronique,Toullec, Patrick Y.
supporting information, p. 1181 - 1186 (2018/04/16)
Lewis bases were evaluated as catalysts for halocarbocyclization reactions of alkynylstyrenes and a cinnamylaniline derivative. Phosphines and phosphorus chalcogenides exhibited high activity for the conversion of alkynylstyrenes in the presence of N -halosuccinimides with up to a 30-fold increase of the initial reaction rate with respect to the background reaction. Phosphorus sulfides and selenides showed the best catalytic activity for the iodocarbocyclization of a cinnamylaniline derivative in the presence of diiodohydantoin. An asymmetric variant of the iodocarbocyclization reaction of an alkynylstyrene using a chiral phosphorus selenide resulted in a modest enantioselectivity.
Palladium-Catalyzed Cross-Coupling of Silyl Electrophiles with Alkylzinc Halides: A Silyl-Negishi Reaction
Cinderella, Andrew P.,Vulovic, Bojan,Watson, Donald A.
supporting information, p. 7741 - 7744 (2017/06/21)
We report the first example of a silyl-Negishi reaction between secondary zinc organometallics and silicon electrophiles. This palladium-catalyzed process provides direct access to alkyl silanes. The delicate balance of steric and electronic parameters of the employed DrewPhos ligand is paramount to suppressing isomerization and promoting efficient and selective cross-coupling.
