X‐Ray‐diffraction analysis of tBu2CN SCl ( 4b ) revealed an almost linear CNS unit with an SN bond order of ca. 1.9 (Fig. 1), in agreement with the structure of a 1‐thia‐2‐azoniaallene chloride. With SCl2 and SbCl5, compound 4b was transformed into the imidosulfurous dichloride 6 (Scheme 2). With morpholine, compounds 4b and 6 afforded the sulfenamide 7 and the aminosulfonium salt 8 , respectively. The (diarylmethylene)amidosulfenyl chlorides 4g , h , i reacted with SbCl5 to give SbCl salts of the 1,2‐benzisothiazoles 9a , b , d , most likely via 1‐thia‐2‐azoniaallene intermediates 2 (Scheme 3). 相似文献
A series of stable imino(chalcogeno)phosphoranes R P( X) NAr, RPh, 2, 4, 6-Me3C6H2, 2, 4, 6-i-Pr3C6H2; Ar 2, 4, 6-t-Bu3C6H2; X S, Se ( 5bd, 6b,c ), has been prepared by the oxidation of λ3-imino-phosphines R P N Ar ( 4b-d ) with sulfur and selenium. When P (tert-butyl)iminophosphine, t-Bu P N- Ar ( 4a ), was reacted with S8 and Seiv the corresponding oligomeric metaphosphonimidates 7, 8 were obtained. All new compounds are characterized by their NMR spectra. The constitution of the imino(thioxo)phosphorane 5d is proved by X-ray crystal structure determination. 相似文献
Summary: The laser irradiation at 193 nm of a gaseous mixture of carbon disulfide and ethene induces the copolymerization of both compounds and affords the chemical vapour deposition of a C/S/H polymer, the composition of which indicates the reaction between two to three CS2 molecules and one C2H4 molecule. Polymer structure is interpreted on the basis of X‐ray photoelectron and FT‐IR spectra as consisting of >CS, >CC<, CH2 CH2 , (CC)SnC4 − n, C (CS) S , S (CS) S , and C S S C configurations. The gas‐phase copolymerization of carbon disulfide and ethene represents the first example of such a reaction between carbon disulfide and a common monomer.
Scheme showing the expected reaction of excited CS2 molecules with other CS2 molecules to form dimers, which then react with another CS2 molecule or add to ethene. 相似文献
RuS4Cl12 and Ru2S6Cl16, Two New Ruthenium(II) Complexes with SCl2 Ligands Ru powder was reacted with SCl2 in closed silika ampoules at 140 °C. From the black solution three compounds RuS4Cl12 1 , Ru2S6Cl16 2 , and Ru2S4Cl13 3 could be crystallized and characterized by x ray analysis. Black crystals of 1 (monoclinic, a = 9.853(1) Å, b = 11.63(1) Å, c = 15.495(1) Å, β = 105.23(1)°, space group P21/c, z = 4) are identified as Trichlorsulfonium‐tris(dichlorsulfan)trichloro‐ruthenat(II) SCl3[RuCl3(SCl2)3]. In the structure the complex anions fac‐[RuCl3(SCl2)3]– and the cations [SCl3]+ are connected to ion pairs by three chlorine bridges. The brown crystals of 2 (triclinic, a = 7.754(2) Å, b = 7.997(2) Å, c = 10.708(2) Å, α = 103.74(3)°, β = 98.44(3)°, γ = 108.58(3)°, space group P‐1, z = 1) contain the binuclear complex Bis‐μ‐chloro‐dichloro‐hexakis(dichlorsulfan)‐diruthenium(II), (SCl2)3ClRu(μ‐Cl)2RuCl(SCl2)3 with two fac‐RuCl3(SCl2)3‐units connected by two chlorine bridges. 3 was identifyed as a known mixed valence Ru(II,III) binuclear complex [Cl2(SCl2)Ru(μ‐Cl)3Ru(SCl2)3]. The vibrational spectra and the thermal behaviour of the compounds are discussed. 相似文献
Organocalcium compounds have been reported as efficient catalysts for various alkene transformations. In contrast to transition metal catalysis, the alkenes are not activated by metal–alkene orbital interactions. Instead it is proposed that alkene activation proceeds through an electrostatic interaction with a Lewis acidic Ca2+. The role of the metal was evaluated by a study using the metal‐free catalysts: [Ph2N−][Me4N+] and [Ph3C−][Me4N+]. These “naked” amides and carbanions can act as catalysts in the conversion of activated double bonds (CO and CN) in the hydroamination of Ar NCO and R NCN R (R=alkyl) by Ph2NH. For the intramolecular hydroamination of unactivated CC bonds in H2CCHCH2CPh2CH2NH2 the presence of a metal cation is crucial. A new type of hybrid catalyst consisting of a strong organic Schwesinger base and a simple metal salt can act as catalyst for the intramolecular alkene hydroamination. The influence of the cation in catalysis is further evaluated by a DFT study. 相似文献
The Schiff base ligand in the title complex, [Pt(C9H8BrN2S2)2], is deprotonated from its tautomeric thiol form and coordinated to PtIIvia the mercapto S and β–N atoms. The configuration about PtII is a perfect square‐planar, with two equivalent Pt—N [2.023 (3) Å] and Pt—S [2.293 (1) Å] bonds. The phenyl ring is twisted against the coordination moiety Pt1/N1/N1′/S2′/S2 by 31.8 (2)°, due to the steric hindrance induced by ortho‐substituted bulky Br atom. 相似文献
A series of NCO/NCS pincer precursors, 3‐(Ar2OCH2)‐2‐Br‐(Ar1N?CH)C6H3 ((Ar1NCOAr2)Br, 3a , 3b , 3c , 3d ) and 3‐(2,6‐Me2C6H3SCH2)‐2‐Br‐(Ar1N?CH)C6H3 ((Ar1NCSMe)Br, 4a and 4b ) were synthesized and characterized. The reactions of [Ar1NCOAr2]Br/ [Ar1NCSMe]Br with nBuLi and the subsequent addition of the rare‐earth‐metal chlorides afforded their corresponding rare‐earth‐metal–pincer complexes, that is, [(Ar1NCOAr2)YCl2(thf)2] ( 5a , 5b , 5c , 5d ), [(Ar1NCOAr2)LuCl2(thf)2] ( 6a , 6d ), [(Ar1NCOAr2)GdCl2(thf)2] ( 7 ), [{(Ar1NCSMe)Y(μ‐Cl)}2{(μ‐Cl)Li(thf)2(μ‐Cl)}2] ( 8 , 9 ), and [{(Ar1NCSMe)Gd(μ‐Cl)}2{(μ‐Cl)Li(thf)2(μ‐Cl)}2] ( 10 , 11 ). These diamagnetic complexes were characterized by 1H and 13C NMR spectroscopy and the molecular structures of compounds 5a , 6a , 7 , and 10 were well‐established by X‐ray diffraction analysis. In compounds 5a , 6a , and 7 , all of the metal centers adopted distorted pentagonal bipyramidal geometries with the NCO donors and two oxygen atoms from the coordinated THF molecules in equatorial positions and the two chlorine atoms in apical positions. Complex 10 is a dimer in which the two equal moieties are linked by two chlorine atoms and two Cl? Li? Cl bridges. In each part, the gadolinium atom adopts a distorted pentagonal bipyramidal geometry. Activated with alkylaluminum and borate, the gadolinium and yttrium complexes showed various activities towards the polymerization of isoprene, thereby affording highly cis‐1,4‐selective polyisoprene, whilst the NCO? lutetium complexes were inert under the same conditions. 相似文献
An efficient two‐step synthesis of the first NHC‐stabilized disilavinylidene (Z)‐(SIdipp)SiSi(Br)Tbb ( 2 ; SIdipp=C[N(C6H3‐2,6‐iPr2)CH2]2, Tbb=C6H2‐2,6‐[CH(SiMe3)2]2‐4‐tBu, NHC=N‐heterocyclic carbene) is reported. The first step of the procedure involved a 2:1 reaction of SiBr2(SIdipp) with the 1,2‐dibromodisilene (E)‐Tbb(Br)SiSi(Br)Tbb at 100 °C, which afforded selectively an unprecedented NHC‐stabilized bromo(silyl)silylene, namely SiBr(SiBr2Tbb)(SIdipp) ( 1 ). Alternatively, compound 1 could be obtained from the 2:1 reaction of SiBr2(SIdipp) with LiTbb at low temperature. 1 was then selectively reduced with C8K to give the NHC‐stabilized disilavinylidene 2 . Both low‐valent silicon compounds were comprehensively characterized by X‐ray diffraction analysis, multinuclear NMR spectroscopy, and elemental analyses. Additionally, the electronic structure of 2 was studied by various quantum‐chemical methods. 相似文献