Synthesis and characterisation of triselenocarbonate [CSe3]2- complexes

[Pt(CSe3)(PR3)2] (PR3= PMe3, PMe2Ph, PPh3, P(p-tol)3, 1/2 dppp, 1/2 dppf) were all obtained by the reaction of the appropriate metal halide containing complex with carbon diselenide in liquid ammonia. Similar reaction with [Pt(Cl)2(dppe)] gave a mixture of triselenocarbonate and perselenocarbonate complexes. [{Pt(mu-CSe3)(PEt3)}4] was formed when the analogous procedure was carried out using [Pt(Cl)2(PEt3)2]. Further reaction of [Pt(CSe3)(PMe2Ph)2] with [M(CO)6] (M = Cr, W, Mo) yielded bimetallic species of the type [Pt(PMe2Ph)2(CSe3)M(CO)5] (M = Cr, W, Mo). The dimeric triselenocarbonate complexes [M{(CSe3)(eta5-C5Me5)}2] (M = Rh, Ir) and [{M(CSe3)(eta6-p-MeC6H4(i)Pr)}2] (M = Ru, Os) have been synthesised from the appropriate transition metal dimer starting material. The triselenocarbonate ligand is Se,Se' bidentate in the monomeric complexes. In the tetrameric structure the exocyclic selenium atoms link the four platinum centres together.     

Synthesis and Structural Characterization of the Complex 〔Et_4N〕_2〔Ni_2(C_2S_4)(C_3S_5)_2〕

１ＩＮＴＲＯＤＵＣＴＩＯＮＴｈｅｃｈｅｍｉｓｔｒｙｏｆｃｏｍｐｏｕｎｄｓｗｉｔｈｄｍｉｔ（ｄｍｉｔ＝１,３ ｄｉｔｈｉｏｌｅ ２ ｔｈｉｏｎｅ ４,５ ｄｉｔｈｉｏｌａｔｅ）ｈａｓａｔｒａｃｔｅｄｃｏｎｓｉｄｅｒａｂｌｅａｔｅｎｔｉｏｎｒｅｃｅｎｔｌ...     

Antibacterial activity of [1Fe-2S]- and [2Fe-2S]-nitrosyl complexes as nitric oxide donors

Russian Chemical Bulletin - The biological activity of a series of sulfur-nitrosyl iron complexes (NICs) depends on the structure of the ligands and the position of the functional groups in the...     

簇合物[Et4N]2[Mo2S4(SCH2CH2S)2]的合成及晶体结构

以(NH4)2MoS4,Et4NBr,HSCH2CH2SH为原料合成了新的簇合物——[Et4N]2[Mo2S4(SCH2CH2S)2],其结构经X射线四圆衍射仪,IR。UV及元素分析确证。其晶体属单斜晶系。晶胞参数为：a=1．0304(8)nm,b=1．4158(8)sin。c=1．1417(1)nm,V=1．63801nm^3,z=4。晶体结构经块状矩阵最小二乘法修正后,最终偏离因子R=0．084。     

Synthesis of 2-dichloromethyl-2-methyl [2-14C]-1,3-dioxolane

The labelled compound was prepared by chlorination of [2-¹⁴C]acetone obtained from the barium salt of [1-¹⁴C]acetic acid by pyrolysis. The reaction product 1,1-dichloro [2-¹⁴C]acetone was converted to 2-dichloromethyl-2-methyl [2-¹⁴C]-1,3-dioxolane by condensation with ethylene glycol in the presence of thionyl chloride. Radiochemical yield: 62% based on [1-¹⁴C]acetic acid.     

Synthesis and crystal structure of the molecules of 1-(2-benzothiazolyl)-3,5-dimethylpyrazole C12H11N3S and dioxodichloro[1-(2-benzothiazolyl)-3,5-dimethylpyrazole]molybdenum(VI) [MoO2(C12H11N3S)Cl2]

N. S. Kurnakov Institute of General and Inorganic Chemistry, Academy of Sciences of the USSR. Scientific-Research Institute of, Physical and Organic Chemistry, Rostov State University. Voroshilovgrad Mechanical Engineering Institute. Translated from Zhurnal Strukturnoi Khimii, Vol. 31, No. 5, pp. 45–53, September–October, 1990.     

Nickel complexes of bidentate [S2] and [SN] borato ligands

Nickel(II) complexes of the monoanionic borato ligands [Ph2B(CH2SCH3)2] (abbreviated Ph2Bt), [Ph2B(CH2S(t)Bu)2] (Ph2Bt(tBu)), [Ph2B(1-pyrazolyl)(CH2SCH3)], and [Ph2B(1-pyrazolyl)(CH2S(t)Bu)] have been prepared and characterized. While [Ph2Bt] formed the square planar homoleptic complex, [Ph2Bt]2Ni, the larger [S2] ligand with tert-butyl substituents, [Ph2BttBu], yielded an unexpected organometallic derivative, [Ph2Bt(tBu)]Ni(eta2-CH2SBut), resulting from B-C bond rupture. The analogous thiametallacycle derived from the [S3] ligand, [PhB(CH2S(t)Bu)3] (PhTt(tBu)), has been structurally authenticated (Schebler, P. J.; Mandimutsira, B. S.; Riordan, C. G.; Liable-Sands, L.; Incarvito, C. D.; Rheingold, A. L. J. Am. Chem. Soc. 2001, 123, 331). The [SN] borato ligands formed exclusively the cis stereoisomers upon reaction with Ni(II) sources, [Ph2B(1-pyrazolyl)(CH2SR)]2Ni. Analysis of the Ni(II/I) reduction potentials by cyclic voltammetry revealed a approximately 600 mV anodic shift upon replacement of two thioether donors ([Ph2Bt]2Ni) with two pyrazolyl donors ([Ph2B(1-pyrazolyl)(CH2SCH3)]2Ni) consistent with the all thioether environment stabilizing the lower oxidation state of nickel.     

Synthesis and structure of [An(RO)PS2]- complexes

Reaction of An(S)PS(2)P(S)An with NaOR [R = Me, Et, (i)Pr] gives the non-symmetric phosphonodithioato anions [An(RO)PS(2)](-) which can be complexed to a range of metals. The group 10 metals (Ni, Pd and Pt) adopt square planar ML(2) complexes. The zinc and cadmium complexes adopt isostructural dimeric M(2)L(4) structures whilst mercury complexes adopt a subtly different dimeric motif. Two distinctly different lead complexes are reported, one consisting of PbL(2) units joined by Pb...S interactions to form distinct dimeric pairs, the other being a completely new structural motif for complexes of this type, PbL(2) units held together by covalently bonded bridging ligands to form an infinite polymeric chain structure. All new compounds have been characterised spectroscopically and nine demonstrative X-ray structures are reported.     

Synthesis of [1, 2-13C2]-S-Lysine Hydrochloride

Cobalt catalyzed hydroformylation-amidocarbonylation of 3-cyanopropene by carbon-13 monoxide and acetamide produced a [1,2-¹³C₂]-labelled mixture of 5-cyano-2-acetamidopentanoic acid and 4-cyano-3-methyl-2-acetamidobutanoic acid (n to b ratio of 7 to 3. 55% yield). Acylase I resolution of this mixture gave the free S-amino acids which could be separated by crystallization. Catalytic reduction of the cyano group of the straight chain acid furnished [1,2-¹³C₂] -S-lysine. HCl.     

Copper(II) complexes of potentially terdentate N2-[(R)-2-hydroxypropyl]- and N2-[(S)-2-hydroxypropyl]-(S)-phenylalaninamide for chiral recognition: Synthesis of the Ligands and Formation Constants

Copper(II) complexes of the ligands N²-[(R)-2-hydroxypropyl]- and N²-[(S)-2-hydroxypropyl]-(S)-phenylalaninamide performed chiral separation of N-dansyl-protected and unmodified amino acids in HPLC (reversed phase). With the aim of investigating which species are potentially involved in the discrimination mechanism, the two ligands were synthesized and their complexation equilibria with Cu²⁺ studied by potentiometry and spectrophotometry in aqueous solution up to pH 11.7. The formation constants of the species observed, [CuL]²⁺, [CuL₂]²⁺, [CuLH_–1]⁺, [CuL₂H_–1]⁺, [CuL₂H_–2], and [CuL₂H_–3]^?, were quite similar for both compounds and were compared to those of (S)-phenylalaninamide. Most probably, in [CuL₂H_–3]^? the ligands behave as terdentate, with the deprotonated OH group occupying an apical position.     

Synthesis of N,N,N-Triethyl-2-[4-(2-phenylethenyl) phenoxy] ethanammonium iodide

The synthesis of N,N,N-triethyl-2-[4-(2-phenylethenyl) phenoxy] ethanammonium iodide, antispasmodic disubstituted olefin, was achieved via palladium-catalyzed cross-coupling of phenylacetylide with aryl bromide followed by hydroalumination.     

Synthesis and structure of novel [Ph(RO)PSe2]- complexes

Reaction of (PhPSe2)2(Woollins reagent) with NaOR (R = Me, Et, (i)Pr) gives the non-symmetric phosphonodiselenoato anions [Ph(RO)PSe2]- which can be complexed to a range of metals. The nickel complex Ni[Ph(MeO)PSe2]2 adopts a square-planar ML2 structure while the cadmium complex Cd[Ph(MeO)PSe2]2 displays a dimeric M2L4 structure. Two different lead complexes are observed, one consisting of PbL2 units joined by Pb...Se interactions to form distinct dimeric pairs. The other displays a novel dimeric structure built around a central four-membered Pb2Se2 ring. All new compounds have been characterised spectroscopically (31P, 1H, 13C NMR, IR, mass spectroscopy), by elemental analysis and five demonstrative X-ray structures are reported.     

4-溴-N,N-二(2-氨基苯氧乙基)苯胺的合成

以对溴苯胺为原料,经4步反应合成了4-溴-N,N-二(2-氨基苯氧乙基)苯胺,其结构经1H NMR, IR和MS表征.     

Synthesis and properties of Ph2S(=N-(Ph2)S[triple bond]N)2

A new type of lambda6-sulfanenitrile with an SN triple bond at both ends, Ph2S(=N-(Ph2)S[triple bond]N)2 (5), was prepared in excellent yield from the one-pot synthesis of diphenylsulfimide (Ph2SNH) with fluoro(diphenyl)-lambda6-sulfanenitrile (Ph2FSN) in the presence of 1,8-diazabicyclo[5.4.0]undec-7-ene. Its molecular structure was determined by X-ray crystallographic analysis. Compound 5 reacted further with methyl triflate and trifluoromethanesulfonic anhydride to afford the corresponding bis-N-methylated and -N-sulfonated compounds.     

双电荷离子[C12H12N2O]2+和[C12H12N2S]2+的气相单分子分解反应研究

The unimolecular dissociation reactions of doubly charged ions were reported,which resulted from a tandem mass spectrometer and a reversed geometry double focusing mass spectrometer by electron impact.Mass analyzed ion kinetic energy spectrometry(MIKES) was used to obtain the kinetic energy releases in charge separation reactions of doubly charged ions.The intercharge distances between the two charges at transition states can be calculated from the kinetic energy releases.Transition structures of unimolecular dissociation reactions were infered from MIKES and MS/MS.