52653-84-6Relevant academic research and scientific papers
Synthesis and molecular structures of tris(thio- and selenophenyl)stannyl complexes of cyclopentadienylcarbonylnitrosylmanganese and their reaction products with tungsten carbony
Pasynskii,Blokhin,Torubaev,Dobrokhotova, Zh. V.
, p. 879 - 886 (2012/03/13)
Reactions of CpMn(CO)(NO)SnCl3 (I) with sodium benzenethiolate and sodium benzenesele-nolate gave orange crystals of the complexes CpMn(CO)(NO)Sn(EPh)3, where E = S (II) or Se (III). Treatment of complex II with photochemically generated W(CO)5(THF) yielded the adduct CpMn(CO)(NO)Sn(SPh)3 ? W(CO)5 (IV). A similar treatment of complex III resulted in the formation of the ditungsten complex W2(CO)4(SePh)6 (V) with transfer of all chalcogenate groups from tin to tungsten. In reactions of complexes II and III with a Pt0 complex with phosphine and acetylene, (PPh 3)2Pt(Ph2C2), the chalcogenate groups are transferred from tin. Only the known Pt(II) complexes (PPh 3)2Pt(EPh)2), where E= S (VI) or Se (VII). Molecular structures IV and V were characterized by X-ray diffraction. It has been found that the Mn-Sn bond in complex IV (2.5479(9) A) is nearly the same length as that found earlier for complex II (2.5328(17) A) and is substantially shorter than the sum of the covalent radii of Mn and Sn (2.78 A). The Sn-S bond is noticeably lengthened (2.5217(11) A) only for the S atom bound to tungsten (W-S, 2.5696(12) A), while the other Sn-S bonds (2.4413(12) and 2.4291(12) A) are virtually the same as in complex II (on average, 2.441 A). Complex V contains the direct W-W bond (2.8153(16) A) supplemented with four benzeneselenolate bridges in which the W-Se bonds (on average, 2.642(2) A) are longer than the two terminal W-SePh bonds (2.571(2) A). All the W-Se bonds are much shorter than the sum of the covalent radii of W and Se (2.82 A).
Mechanistic investigation and new catalyst design in palladium- and platinum-catalyzed Se-Se bond addition to alkynes
Ananikov, Valentine P.,Beletskaya, Irina P.,Aleksandrov, Grigory G.,Eremenko, Igor L.
, p. 1414 - 1421 (2008/10/08)
The present study explains the different catalytic activities of platinum and palladium in Se - Se addition reactions with alkynes. Under the catalytic conditions cis-[Pt(SePh)2(PPh3)2] undergoes fast isomerization to the
Palladium and platinum catalyzed hydroselenation of alkynes: Se-H vs Se-Se addition to C≡C bond
Ananikov, Valentine P.,Malyshev, Denis A.,Beletskaya, Irina P.,Aleksandrov, Grigory G.,Eremenko, Igor L.
, p. 162 - 172 (2007/10/03)
A mechanistic study of the hydroselenation of alkynes catalyzed by Pd(PPh3)4 and Pt(PPh3)4 has shown that the palladium complex gives products of both Se-H and Se-Se bond addition to the triple bond of alkynes, while the platinum complex selectively catalyzes Se-H bond addition. The key intermediate of PhSeH addition to the metal center, namely Pt(H)(SePh)(PPh3)2, was detected by 1H-NMR spectroscopy. The analogous palladium complex rapidly decomposes with evolution of molecular hydrogen. A convenient method was developed for the preparation of Markovnikov hydroselenation products H2C=C(SePh)R, and the scope of this reaction was investigated. The first X-ray structure of the Markovnikov product H2C=C(SePh)CH2N+ HMe2·HOOC=COO- is reported.
Aryl chalcogenolates of palladium(II) and platinum(II): Synthesis and structure
Gupta, Sushil K.,Khandelwal, Bishan L.
, p. 977 - 981 (2007/10/02)
Complexes of the type (I), (II) and (III) have been synthesized from the reactions between cis- and NaSeAr, and between and NaEAr (generated in situ) in ethanol-benzene at room temperature.Their structures have been established on the basis elemental analyses, conductance and molecular weight measurements, and IR, 1H and 31P NMR spectra.A trans-form for I and II and a cis-form for III have been assigned.The reaction of III (M = Pt; Ar = Ph) with has led to the formation of an interesting class of hetero binuclear complexes(DPPE)Pt(μ-EPh)2PdCl2> (IV) with phenyl chalcogen bridging.
Fe2(μ-E2)(CO)6 (E = S, Se, and Te) as Reagents for the Preparation of Mixed-Metal Chalcogenide Clusters
Day, Victor W.,Lesch, David A.,Rauchfuss, Thomas B.
, p. 1290 - 1295 (2007/10/02)
The compounds Fe2(μ-E2)(CO)6, where E = S, Se, and Te, react efficiently with Pt(PPh3)2C2H4 to afford the new heterometallic clusters, (CO)6Fe2(μ-E)2Pt(PPh3)2.This reaction formally involves the homolytic cleavage of the E-E bond in the μ-E2 precursor complexes and represents a novel route to mixed-metal clusters. 13P NMR of (PPh3)(CO)5Fe2(μ-S)2Pt(PPH3)2 (prepared from Fe2(μ-S2)(CO)5(PPh3) indicates that the plane of the Pt coordination sphere is perpendicular to the iron-iron vector.The structure of (CO)6Fe2(μ3-Se)2Pt(PPh3)2 was determined by conventional X-ray crystallographic techniques.The crystals were monoclinic with a = 10.944(2) Angstroem, b = 16.321(3) Angstroem, c = 23.135(4) Angstroem, β = 94.68(1) deg, Z = 4; the space group is P21/n.Conventional full-matrix least-squares refinement with nonhydrogen atoms anisotropic and fixed hydrogen atoms isotropic gave R1 = 0.037 and R2 = 0.040 for 7119 reflections having 2θ Mo Kα/ 3?(I).The structure consists of an isosceles triangle of metal atoms tethered by two capping μ3-Se moieties.The two Fe(CO)3 units are mutually bonded, and this fragment closely resembles Fe2(μ-Se2)(CO)6 with an expanded Se-Se vector.We reconcile the reactivity of these μ-E2 compounds and the chemical dormancy of species such as Ph2Te2 and monometallic S2 complexes as being both electronic and steric (ring strain) in origin.
