Preparation of Re(I)- and (99m)Tc(I)-metallocarboranes in water under weakly basic reaction conditions

A new method for the preparation of Re- and (99m)Tc-metallocarboranes in water under mild reaction conditions was developed. Three nido-carborane ligands were reacted with [Re(CO)(3)Br(3)](2)(-) in the presence of aqueous potassium fluoride to give the corresponding eta(5)-Re(CO)(3)-carborane complexes. The use of KF as a base afforded the desired Re-metallocarboranes in good yields while avoiding the formation of Re clusters, which are byproducts commonly observed when reactions are carried out in the presence of strong aqueous bases. The reaction was also performed at the tracer level producing the first (99m)Tc-carborane complex, which was isolated in 80% radiochemical yield following a simple Sep-Pak purification process. The resulting organometallic complex was stable to cysteine and histidine challenges for more than 24 h.     

Bis(ortho-)chelated Monoanionic Bisphosphinoaryl Ruthenium(II) Complexes: Synthesis, Characterization and Reactivity

ＩｎｔｒｏｄｕｃｔｉｏｎＴｈｅｉｎｔｅｒａｃｔｉｏｎｏｆｂｉｓｐｈｏｓｐｈｉｎｅｓｗｉｔｈ (ｔｒａｎｓｉｔｉｏｎ)ｍｅｔａｌｓｉｓａｆａｓｃｉｎａｔｉｎｇｆｉｅｌｄｆｒｏｍｔｈｅｃｏｏｒｄｉｎａｔｉｏｎｃｈｅｍｉｓｔ’ｓｐｏｉｎｔｏｆｖｉｅｗ .Ａｗｉｄｅａｒｒａｙｏｆｍｏｎｏ ａｎｄｍｕｌｔｉ ｍｅｔａｌｌｉｃｃｉｓ η2 Ｐ ,Ｐ′ｃｏｏｒｄｉｎａｔｅｄｃｏｍｐｌｅｘｅｓａｒｅｆｏｒｍｅｄｉｎｗｈｉｃｈａｖａｒｉｅｔｙｏｆｃｏｏｒｄｉｎａｔｉｏｎｍｏｄｅｓｉｓｅｎ ｃｏｕｎｔｅｒｅｄ .Ｔｈｅｃｈｅｌａ…     

Synthesis of ortho- and para-quinones of the benzindole series

Ethyl esters of -(3-chloro-1,4-naphthoquinon-3-yl)crotonic or cinnamic acids were obtained by the reaction of 2,3-dichloro-1,4-naphthoquinone with ethyl esters of N-substituted -aminocrotonic or -aminocinnamic acids. These esters were converted by alkaline fusion into benz[f]indole-4,9-dione-3-carboxylic acids, and into ethyl esters of benz[g]indole-4,5-dione-3-carboxylic acid by the action of acetic acid.Deceased.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 1, pp. 66–68, January, 1989.     

Synthesis and anticancer properties of gold(I) and silver(I) N-heterocyclic carbene complexes

Bis(1,3-dimethylimidazol-2-ylidene)silver(I) nitrate and bis(4,5-dichloro-1,3-dimethylimidazol-2-ylidene)silver(I) nitrate were prepared by reacting the corresponding imidazolium nitrate salts with silver oxide. Bis(1,3-dimethylimidazol-2-ylidene)gold(I) nitrate and bis(4,5-dichloro-1,3-dimethylimidazol-2-ylidene)gold(I) nitrate salts were prepared via transmetallation of their silver precursors with chloro dimethylsulfide gold. The anticancer properties were determined using NCI-H460 lung cancer cells. Efficacy was established by comparison of the gold and silver compounds with cisplatin.     

Synthesis and Structures of Silver(I) and Copper(I) 3,5-Dipentyl-1,2,4-Triazolates

The Ag(I) and Cu(I) complexes of 4-amino-3,5-dipentyl-4H-1,2,4-triazole (4-NH₂-3,5-(C₅H₁₁)₂tz) and 3,5-dipentyl-1H-1,2,4-triazole (3,5-(C₅H₁₁)₂tzH) have been synthesized and characterized. X-Ray analysis shows that {Ag₄[4-NH₂-3,5-(C₅H₁₁)₂tz]₆}(BF₄)₄ is a tetranuclear complex featuring an Ag₄tz₆ cluster; {Ag[3,5-(C₅H₁₁)₂tz]}_n exhibits a 3D structure of lvt-a topology; and {Cu₂[3,5-(C₅H₁₁)₂tz]Br}_n is a Cu₄Br₄-cluster based 3D complex with the dia topology.     

Synthesis and Study of Thiocyanato(N)iodocuprates(I) and -Argentates(I) of Quaternary Arsonium Cations

The reactions of triarylalkylarsonium acetates with CuI and AgI in the presence of excess potassium thiocyanate yield the corresponding triarylalkylarsonium thiocyanato(N)iodocuprates(I) and -argentates(I). The composition, structure, and thermal behavior (in the range 20–1000°C) of these compounds were studied by chemical analysis, IR spectroscopy, conductometry, and differential thermal analysis.__________Translated from Zhurnal Obshchei Khimii, Vol. 75, No. 5, 2005, pp. 738–741.Original Russian Text Copyright © 2005 by Gigauri, Kikalishvili, Kipiani, Khidesheli, Kutsiya.     

Synthesis of thionato(trimethylphosphine)gold(I) complexes

Summary New compounds of formula [AuL(PMe₃)]Cl [L = imidazolidine-2-thione (Imt), 1,3-diazinane-2-thione (Diaz), 1,3-diazepine-2-thione (Diap) and their derivatives] have been synthesized and characterized by elemental analysis, and i.r., ¹³C- and ³¹P-n.m.r. spectroscopies. The Diap ligand, which incorporates the thione in a seven-membered heterocyclic ring, binds more strongly to Au^I compared to its Diaz (six-membered ring) and Imt (five-membered ring) analogues.     

Synthesis of Cu(I) octamolybdates using tetrakis-acetonitrilecopper(I) hexafluorophosphate

Reaction of (NBu₄)₂[Mo₂O₇] with [Cu(CH₃CN)₄](PF₆) in acetonitrile results in isolation of the orange β-octamolybdate [Cu(CH₃CN)₄]₂[Mo₈O₂₆Cu₂(CH₃CN)₄] (1) along with the colourless α-octamolybdate [Cu(CH₃CN)₄]₄[Mo₈O₂₆]·2CH₃CN (2). Both products decompose rapidly upon removal from their mother liquors, forming an insoluble, dark brown coloured phase with the composition Cu₄[Mo₈O₂₆]·0.6CH₃CN·16H₂O (3). The copper(I) acetonitrile derivatised isopolyanion in 1 thus represents an intermediate structure between the simple, underivatised octamolybdate 2 and fully condensed, polymeric phase 3.     

Synthesis of N,O-heterocyclic carbene and coordination to rhodium(I) and copper(I)

5,7-Di-tert-butyl-3-phenyl benzoxazolium tetrafluoroborate 1 could be prepared by simple reaction of the corresponding aminophenol with triethyl orthoformate under acidic conditions. Both rhodium(I) and copper(I) complexes with benzoxazol-2-ylidene ligand were then efficiently synthesised in a straightforward and smooth manner involving the reaction of benzoxazolium salt 1 with metal precursor and an external base. The complexes have been fully characterised and used in metal-catalysed hydrosilylation of ketones, where they showed poor catalytic activity, presumably due to low stability of the complexes under those conditions.     

Synthesis and Structural Characterization of Gallium(I) and Indium(I) Cations Coordinated by Pentamethylethylenediamine

Herein we report on the facile access to a Ga^I and In^I complex salt of pentamethyldiethylenetriamine (PMDTA) with the weakly coordinating counterion [Al(OR^F)₄]^– [R^F = C(CF₃)₃]. Thus, the low temperature reaction of [M(PhF)₂]⁺ (M = Ga, In) solutions in 1,2-F₂C₆H₄ (oDFB) with PMDTA yielded the title compounds M(PMDTA)⁺[Al(OR^F)₄]^– (M = Ga 1 , in 2 ) in non-optimized yields. Both compounds are highly sensitive towards air and moisture, have a rather limited lifetime at room temperature, but were structurally characterized.     

Synthesis and properties of Rh(I) and Ir(I) distibine complexes with organometallic co-ligands

The first series of Rh(I) distibine complexes with organometallic co-ligands is described, including the five-coordinate [Rh(cod)(distibine)Cl], the 16-electron planar cations [Rh(cod)(distibine)]BF4 and [Rh{Ph2Sb(CH2)3SbPh2}2]BF4 and the five-coordinate [Rh(CO)(distibine)2][Rh(CO)2Cl2] (distibine=R2Sb(CH2)3SbR2, R=Ph or Me, and o-C6H4(CH2SbMe2)2). The corresponding Ir(I) species [Ir(cod)(distibine)]BF4 and [Ir{Ph2Sb(CH2)3SbPh2}2]BF4 have also been prepared. The complexes have been characterised by 1H and 13C{1H} NMR and IR spectroscopy, electrospray mass spectrometry and microanalysis. The crystal structure of the anion exchanged [Rh(CO){Ph2Sb(CH2)3SbPh2}2]PF(6).3/4CH2Cl2 is also described. The methyl-substituted distibine complexes are less stable than the complexes of Ph2Sb(CH2)3SbPh2, with C-Sb fission occurring in some of the complexes of the former. The salts [Rh(CO){Ph2Sb(CH2)3SbPh2}2]PF6 and [Rh{Ph2Sb(CH2)3SbPh2}2]BF4 undergo oxidative addition with Br2 to give the known [RhBr2{Ph2Sb(CH2)3SbPh2}2]+, while using HCl gives the same hydride complex from both precursors, which is tentatively assigned as [RhHCl2{Ph2Sb(CH2)3SbPh2}]. An unexpected further Rh(III) product from this reaction, trans-[RhCl2{Ph2Sb(CH2)3SbPh2}{PhClSb(CH2)3SbClPh}]Cl, was identified by a crystal structure analysis and represents the first structurally characterised example of a chlorostibine coordinated to a metal. [Rh{Ph2Sb(CH2)3SbPh2}2]BF4 reacts with CO to give [Rh(CO){Ph2Sb(CH2)3SbPh2}2]BF4 initially, and upon further exposure this species undergoes further reversible carbonylation to give a cis-dicarbonyl species thought to be [Rh(CO)2{Ph2Sb(CH2)3SbPh2}{kappa1Sb-Ph2Sb(CH2)3SbPh2}]BF4 which converts back to the monocarbonyl complex when the CO atmosphere is replaced with N2.     

Synthesis and reactions of cyano-pentafluorophenyl aurate(I) and -(III)

The preparation of Q[Au(C₆F₅)_n(CN)_m] (Q = bulky cation; n = 1 or 3, m = 1; n = 2, m = 2) is described and the f     

Synthesis of novel Ag(I)-N-heterocyclic carbene complexes soluble in both water and dichloromethane and their antimicrobial studies

Abstract

The interaction of the benzimidazolium salt with Ag₂O in dichloromethane to prepare novel Ag(I)-N-heterocyclic carbene complexes has been carried out at room temperature for 48?h in the absence of light. The obtained complexes were identified and characterized by ¹H and ¹³C NMR, FT-IR and elemental analysis techniques. In addition, it has been found that some of the complexes are antimicrobially active and show higher activity than the free ligand. Probably metal chelation affects significantly the antimicrobial behavior of the ligands. The minimum inhibitory concentration of the complexes was determined. The results indicated that these complexes exhibit antimicrobial activity.     

Synthesis of 3,1-Benzoxazines from N-Substituted ortho-(Cycloalk-1-enyl or alk-2-en-2-yl)anilines

New derivatives of 3,1-benzoxazine have been synthesized by the cyclization of RCO-substituted at the nitrogen atom (R = OEt, Me, NH₂) ortho-(cycloalk-1-enyl or alken-1-yl)anilines under mild conditions.     

Synthesis and Coordination of Tripodal-Containing Copper(I) Complexes

Reaction of copper(I) chloride with 2,2-bis(diphenylphosphinomethyl)-l-phenylthiopropane P₂S produced a dimeric species [(P₂S)CuC1]₂ (2). Treatment of 2 with silver nitrate in acetonitrile gave a hexameric crystalline metal complex {[(P₂S)Cu(CH₃CN)]₆⁺6NO₃} (4), which had a “cyclodextrin-type” structure. A linear polymeric copper complex [(P₂S)Cu(NO₃)]_n was obtained by recrystallization of 4 in chloroform. These complexes were characterized by single crystal analyses, and their coordination behaviors in solution are discussed.     

无机化学综合实验:Cu(I)配合物的合成与光致发光性能

Cu（I）配合物的合成与光致发光性能实验是结合无机化学中的配合物基础知识和前沿研究热点设计的综合性实验,包括配合物的制备和光致发光性质表征。本实验中分别制备了立方烷、阶梯状、二聚体等不同结构和不同配体的Cu（I）配合物,深入研究了光致发光性能与配合物结构之间的关系。该实验共需12学时完成,实验过程包括配合物制备、减压过滤、荧光光谱测试与分析等,涉及沉淀溶解、配位等多种反应类型和分子光物理性质探究。该综合性实验对实验设备要求低,实验现象明显,产率高,教学过程可操作性强,综合性强。教学实践表明,该实验能显著激发学生学习兴趣,不仅可以让学生加深对无机化学基础知识的理解,还可以获取前沿知识,对提高学生的综合实验能力,培养创新型、复合型人才具有重要意义。     

Synthesis and properties of palladium(I) carbonyl chlorides

Palladium(I) carbonyl chloride (PdCOCl) _n has been synthesized by the effect of CO on PdCl₂ in the presence of trace water. Anionic palladium(I) carbonyl chloride has been synthesized during treatment of ethanol-based or acetone-based solutions of H₂PdCI₄ containing small amounts of water; it has been isolated from the solution as the salt Cs₂[Pd₂(CO)₂Cl₄]. IR-spectra, X-ray diffraction patterns, and thermogravimetry data on synthesized palladium(I) carbonyl complexes are presented.