- Salts of Tris(pentafluoroethyl)silylchalcogenolates [Si(C2F5)3E]-with e = S, Se, and Te: Synthesis, Structure, and Reactivity
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Unlike silanolates [SiR3O]- (R = alkyl, aryl), which have been intensely studied, the heavier derivatives [SiR3E]- (E = S, Se, Te) have been much less examined. Among such species, virtually nothing is known about perfluoroalkyl-substituted silylchalcogenolates. In this contribution, a convenient synthesis of tris(pentafluoroethyl)silylchalcogenolate salts [{(Et2N)3P═N}3PN(H)tBu][Si(C2F5)3E] (E = S, Se, Te; tBu = tert-butyl) is presented. All representatives were isolated and fully characterized by multinuclear NMR spectroscopy, IR spectroscopy, mass spectrometry, elemental analysis, and X-ray diffraction studies. Furthermore, first reactivity studies of these novel species toward selected metal halide complexes were performed. In this course, metal complexes [HgPh{SSi(C2F5)3}] (2) and [Au(PPh3){SSi(C2F5)3}] (3) were isolated and characterized.
- Tiessen, Natalia,Schwarze, Nico,Stammler, Hans-Georg,Neumann, Beate,Hoge, Berthold
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supporting information
p. 15112 - 15117
(2021/10/20)
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- A Boric Acid-Functionalized Lanthanide Metal-Organic Framework as a Fluorescence turn-on Probe for Selective Monitoring of Hg2+ and CH3Hg+
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Mercury detection remains an important task because of its high toxicity. Herein a new dual-signal probe based on a boric acid (BA)-functionalized lanthanide metal-organic framework (BA-Eu-MOF) was developed for the detection of Hg2+ and CH3Hg+ ions for the first time. The BA-Eu-MOF was synthesized by coordination of Eu3+ with 5-boronobezene-1, 3-dicarboxylic acid (5-bop) through a one-pot method. The 5-bop ligand not only acted as the antenna to sensitize the luminescence of Eu3+ but also provided reaction sites for Hg2+ and CH3Hg+. Owing to the electron-withdrawing effect of the BA group, the antenna effect of the ligand was passivating and the BA-Eu-MOF showed weak red emission in water. Upon addition of Hg2+ or CH3Hg+ into the system, a transmetalation reaction took place, i.e., BA groups were replaced by Hg2+ or CH3Hg+ therefore, the antenna effect of the ligand was triggered, leading to the enhancement of red emission. As Hg2+ or CH3Hg+ concentration increased, the red emission was gradually enhanced, and the color change was also observed with the naked eye under 365 nm ultraviolet light. Owing to the porous characteristics and the surface effect of the MOF, as well as the unique transmetalation reaction between the BA group and Hg2+ or CH3Hg+, the developed nanoprobe showed excellent characteristics for simultaneous detection of Hg2+ and CH3Hg+, such as simple preparation, convenient operation, turn-on signal output, high sensitivity, and selectivity. The unique features of the BA-Eu-MOF make it an attractive probe for monitoring Hg2+ and CH3Hg+
- Chen, Guang,Kong, Rong-Mei,Liang, Maosheng,Qu, Fengli,Wang, Hao,Wang, Xiuli,Xia, Lian
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p. 3366 - 3372
(2020/03/10)
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- Transmetalation of Pentafluorophenylmercury Derivatives with Organylmagnesium Bromides
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The reactions of pentafluorophenylmercury derivatives with organomagnesium compounds have been studied. The interaction of pentafluorophenylmercury chloride with RMgBr (R = Et, Ph) has afforded diphenyl- and diethylmercury or phenylmercury chloride, besides the expected product (C6F5HgR). The results have been explained by the transmetalation of C6F5HgR with the Grignard reagent, followed by the reaction of the resulting C6F5MgX (X = Br, C6F5) with pentafluorophenylmercury chloride. Transmetalation of (C6F5)2Hg with organylmagnesium bromides has led to the formation of C6F5MgX and R2Hg.
- Bardin
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p. 1406 - 1408
(2019/08/21)
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- Activation of the Hg-C Bond of Methylmercury by [S2]-Donor Ligands
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Here we report that [S2]-donor ligands BmmOH, BmmMe, and BmeMe bind rapidly and reversibly to the mercury centers of organomercurials, RHgX, and facilitate the cleavage of Hg-C bonds of RHgX to produce stable tetracoordinated Hg(II) complexes and R2Hg. Significantly, the rate of cleavage of Hg-C bonds depends critically on the X group of RHgX (X = BF4-, Cl-, I-) and the [S2]-donor ligands used to induce the Hg-C bonds. For instance, the initial rate of cleavage of the Hg-C bond of MeHgI induced by BmeMe is almost 2-fold higher than the initial rate obtained by BmmOH or BmmMe, indicating that the spacer between the two imidazole rings of [S2]-donor ligands plays a significant role here in the cleavage of Hg-C bonds. Surprisingly, we noticed that the initial rate of cleavage of the Hg-C bond of MeHgI induced by BmeMe (or BmmMe) is almost 10-fold and 100-fold faster than the cleavage of Hg-C bonds of MeHgCl and [MeHg]BF4 respectively, under identical reaction conditions, suggesting that the Hg-C bond of [MeHg]BF4 is highly inert at room temperature (21 °C). We also show here that the nature of the final stable cleaved products, i.e. Hg(II) complexes, depends on the X group of RHgX and the [S2]-donor ligands. For instance, the reaction of BmmMe with MeHgCl (1:1 molar ratio) afforded the formation of the 16-membered metallacyclic dinuclear mercury compound (BmmMe)2Hg2Cl4, in which the two Cl atoms are located inside the ring, whereas due to the large size of the I atom, a similar reaction with MeHgI yielded polymeric [(BmmMe)2HgI2]m·(MeHgI)n. However, the treatment of BmmMe with ionic [RHg]BF4 led to the formation of the tetrathione-coordinated mononuclear mercury compound [(BmmMe)2Hg](BF4)2, where BF4- serves as a counteranion.
- Karri, Ramesh,Banerjee, Mainak,Chalana, Ashish,Jha, Kunal Kumar,Roy, Gouriprasanna
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p. 12102 - 12115
(2017/10/24)
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- Homolytic reactive mass spectrometry of fullerenes: Interaction of C 60 and C70 with organo- and organoelement mercurials in the electron impact ion source of a mass spectrometer; EPR, CIDEP, and MS studies of several analogous react
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Interaction of C60 with organo- and organoelement mercurials (CF3HgBr, PhHgBr, P-CH3C6H4HgBr, P-CH3OC6H4HgCl, CF3HgPh, Ph 2Hg, (o-carborane-9-yl)
- Lyakhovetsky, Yury I.,Shilova, Elena A.,Bashilov, Vasily V.,Sokolov, Viatcheslav I.,Nekrasov, Yuri S.,Tumanskii, Boris L.
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p. 13700 - 13710
(2010/05/11)
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- Diphenylmercury, redetermined at 120 K: Sheets built from a single C - H...π(arene) hydrogen bond
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At 120 K, the molecules of the title compound, [Hg(C6H 5)2], lie across centres of inversion in space group P21/n and are linked by a single C - H...π(arene) hydrogen bond into (101) sheets. The same supramolecular structure is found at 298 K.
- Glidewell, Christopher,Low, John N.,Wardell, James L.
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p. m107-m108
(2007/10/03)
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- Influence of metal cation on chromophore properties of complexes of some d metals with α,α-dipyrrolylmethene
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In complexes of Cu2+, Ni2+, Co2+, Zn 2+, and Hg2+ with 3,3′,5,5′-tetramethyl-4, 4′-dibutyl-2,2′-dipyrrolylmethene, the d-metal ion exerts an auxochromic effect on the π system of the ligand, manifested in a bathochromic shift of the first absorption band in the spectrum of the complex, compared to the free ligand. Polarization of the chromophore π system in the complexes increases in the order Zn2+ 2+ 2+ 2+ 2+. The Hg2+ ion in the complex with dipyrrolylmethene participates in mercuration of benzene and chloroform; the reaction with chloroform is faster, with the rates of both reactions strongly depending on temperature. 2004 MAIK Nauka/Interperiodica .
- Guseva,Antina,Berezin,V'yugin
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p. 1282 - 1285
(2007/10/03)
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- Phenylation of Organic Derivatives of Mercury, Silicon, Tin, and Bismuth with Pentaphenylantimony and Pentaphenylphosphorus
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Pentaphenylantimony and -phosphorus react with arylmercury chlorides in toluene at room temperature to give diaryl derivatives of mercury in yields of up to 95%. The reactions of pentaphenylantimony and -phosphorus with silicon and tin halides involve ary
- Sharutin,Sharutina,Senchurin,Egorova,Ivanenko,Petrov
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p. 202 - 203
(2007/10/03)
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- Some reactions of di-and triphenyllanthanides
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Reactions of Ph2Yb(THF)2 and Ph3Ln(THF)3 (Ln = Ho, Tm, Yb) with H2O, PhC≡CH, C5H6, HgX2, and I2 were studied. The phenyl derivatives of lanthanides are highly reactive toward these agents and form expected products in high yields.
- Zheleznova,Bochkarev,Safronova,Zhil'tsov
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p. 784 - 787
(2007/10/03)
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- Synthesis and NMR spectroscopy of dichlorobis(acetophenonethiosemicarbazone) mercury(II) formed from phenylmercury(II) chloride and acetophenonethiosemicarbazone: The first example of symmetrisation in organomercury(II)-thiosemicarbazone chemistry
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The reaction of phenylmercury(II) chloride with acetophenonethiosemicarbazone (Hatsc) in ethanol in 1:1 mole ratio undergoes symmetrisation forming the products, HgCl2(Hatsc)2 and Ph2Hg instead of the anticipated compound PhHgCl(Hatsc). The analytical data, some physical properties, IR and NMR (1H, 13C, 199Hg) spectroscopy all support the formation of HgCl2(Hatsc)2. 199Hg NMR of the solid obtained from the filtrate of the reaction provides evidence for Ph2Hg. This reaction represents the first example of a symmetrisation phenomenon observed in organomercury(II)-thiosemicarbazone chemistry.
- Lobana,Sánchez,Casas,García-Tasende,Sordo
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p. 169 - 172
(2008/10/08)
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- Synthesis and characterization of the linear M - Hg - M trimetallic complexes [η5-Bz5C5 (CO)3M]2Hg and [η5-HO2CC5H4(CO) 3M]2Hg (M = Cr
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The η5-Bz5C5 ligand-containing trimetallic complexes [η5-Bz5C5(CO)3M]2Hg (M = Cr, Mo, W) were synthesized from the in situ reaction of phenylmercuric chloride with cor
- Song, Li-Cheng,Zhang, Lu-Yan,Tao, Zhi-Fu,Hu, Qing-Mei,Huang, Xiao-Ying
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p. 403 - 408
(2008/10/09)
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- Symmetrization of phenylmercuric hydroxides by the action of nickel(II) and cobalt(II) acetylacetonates. Isolation and structural characterization of an intermediate in this reaction
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The complex adducts [M(acac)2(PhHgOHgPh)]2 (M = Co, Ni) have been obtained by incorporation of PhHgOH into the coordination sphere of M(acac)2 at ambient temperature. The X-ray crystal structure of [Ni(acac)2(PhHgOHgPh)(Et2O)]2 (1c) reveals a dimeric nickel complex coordinated by the acetylacetonate oxygen and the bridging oxygen of bis(phenylmercuric) oxide. Refluxing a THF solution of compound 1c gave diphenylmercury, HgO, and Ni(acac)2(THF)2. With PhHgOH or PhHgSH the symmetrization reactions also occurred when catalytic amounts of Ni(acac)2 were used. In contrast, triphenyltin derivatives (hydroxide, acetate, oxide) on treatment with M(acac)2 in aqueous THF gave the stable complexes [M(acac)2(Ph3SnOH)]2 (M = Co, Ni). The structure of [Ni(acac)2(Ph3SnOH)]2 (2) was also determined by X-ray crystallography.
- D?ring, Manfred,Hahn, Gabriela,Stoll, Michael,Wolski, Alexander C.
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p. 1879 - 1883
(2008/10/08)
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- Preparation, spectroscopic properties and thermal stabilities of organomercury compounds containing the bulky ligand (Me3Si)3C or (PhMe2Si)3C
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Mercury compounds of the types HgR1R (R1 = C(SiMe3)3; R = Me, iPr, Bu, tBu or Ph) and HgR2R (R2 = C(SiMe2Ph)3; R = Me, Bu, CH2Ph or Ph) have been prepared. Those containing R1 were made by reactions of the bromides HgR1 Br with the Grignard reagents MgRX, and those containing R2 by reaction of HgR2Cl with LiR or, for R = CH2Ph, with Mg(CH2Ph)Cl. Replacement of one R group in HgR2 by the bulky R1 or R2 group leads to a large increase in thermal stability, a marked shift in the 199Hg resonance to lower frequency and an increase in the coupling constant 1J(13C-199Hg) for the Hg-R bond. The compound HgR2Cl does not react further with LiR2 in tetrahydrofuran, but with LiR1 gives HgR1R2; the arrangement of the SiMe2Ph groups in the latter in solution in CH2Cl2 at low temperature appears to be different from that in the solid.
- Al-Juaid, Salih S.,Eaborn, Colin,Lickiss, Paul D.,Smith, J. David,Tavakkoli, Kayumars,Webb, Alexander D.
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p. 143 - 151
(2007/10/03)
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- Tin/mercury exchange in 1,2-distannyl-1-alkenes and 1-silyl-2-stannyl-1-alkenes
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1,2-Bis(chloromercuri)alkenes, 1-trimethylsilyl-2-chloromercuri-alkenes and 1-trimethylsilyl-2-organomercurialkenes can be readily made by transmetallation of the corresponding trimethyltin compounds with HgCl2 and RHgCl; their structures have been confirmed by multinuclear NMR data.The new compounds are expected to have a large synthetic potential involving lithium/mercury exchange, and subsequent reaction with electrophilic reagents.Key words: Mercury; Nuclear magnetic resonance; Tin; Silicon
- Mitchell, T. N.,Kowall, B.
-
-
- Characterization of Alkyl- and Aryl-mercuric Hydrides by NMR Spectroscopy
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Low-temperature NMR measurements (1H, 13C, 199Hg) confirm that organomercuric hydrides (RHgH; R=alkyl, cycloalkyl, phenyl) are characterisable species in solution.
- Kwetkat, Klaus,Kitching, William
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p. 345 - 348
(2007/10/02)
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- 31P, 77Se and 199Hg NMR spectral studies of phenylmercury(II) complexes with triphenylphosphine and its derivatives
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The solution phase behaviour of complexes of phenyl-mercury (II) halides/pseudohalides/carboxylates with tetriaryphosphines having stoichiometry: PhHgXL (X = Cl, NO3, SCN, O2CR, R = CH3, CF3 or CCl3; L = Ph3P, Ph3PE, E = O, S, Se) has been studied using 31P, 77Se and 199Hg NMR spectroscopy.It has been compared, where possible, with the solid state behaviour of these compounds.Based on 199Hg NMR chemical shifts, a possibility of d?(Hg) d?(P) bonding has been suggested.The order of Hg-ligand interaction appears to be: Ph3P >/= Ph3PSe > Ph3PS > Ph3PO.
- Lobana, Tarlok S.,Sandhu, Maninder Jeet K.
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p. 394 - 396
(2007/10/02)
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- Nucleophilic cleavage of the Si-C bond in organotrifluorosilanes and diorganodifluorosilanes
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The Si-C bond in aryltrifluorosilanes, 4-XC6H4SiF3 (X = H, CH3, Cl, Br or NO2), is readily cleaved by mercury(II) salts HgY2 (Y = Cl, Br, I, CN or OCOCH3) or HgO to form organomercurials of the type 4-XC6H4HgY or (4-XC6H4)2Hg, respectively.Electron-donating substituent X facilitate the reaction, whereas electron-withdrawing substituents make it more difficult.Mercury(II) salts and mercury(II) oxide also cleave the Si-C bond in chloromethyltrifluorosilanes, F3Si(CH3-nCln) (n = 1-3) to produce the corresponding organic mercurials containing an Hg(CH3-nCln) group.The substitution of the fluorine atom in organotrifluorosilanes by an alkyl group hinders the bond cleavage between the silicon atom and the electronegative organic substituent.The reactions studied are believed to follow a nucleophilic mechanism involving asynchronous formation of a four-centered transition state with a pentacoordinate silicon atom.
- Voronkov, M. G.,Chermov, N. F.,Perlova, E. M.
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p. 225 - 230
(2007/10/02)
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- PREPARATION AND X-RAY STRUCTURE OF BIS(PHENYLMERCURIC)OXONIUM TETRAFLUOROBORATE HYDRATE, *H2O
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The reaction of PhHgOH or (PhHg)2O with strong acids gives +, which has been fully characterised as the - salt.The X-ray structure of *H2O shows the cation to have an Hg-O-Hg angle of 126 deg and a Hg...Hg distance of 3.639 Angstroem, which precludes an intramolecular Hg-Hg bonding interaction.
- Nicholson, Brian K.,Whitton, Alan J.
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p. 139 - 144
(2007/10/02)
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- Electrochemical Reduction of Unsymmetrically Substituted Diphenyliodonium Salts at Mercury Cathodes in Dimethylformamide
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A study has been made of the electrochemistry of five unsymmetrically substituted diphenyliodonium salts at mercury cathodes in dimethylformamide containing tetramethylammonium perchlorate.Polarograms indicate that the iodonium cations undergo reduction in three stages: (1) one-electron reduction to yield either (a) iodobenzene and a substituted phenylmercury radical or (b) a substituted iodobenzene and a phenylmercury radical, (2) two-electron reduction of the iodobenzene or substituted iodobenzene, and (3) one-electron reduction of the substituted or unsubstituted phenylmercury radical.When electrolyses are performed at potentials corresponding to the first stage of reduction, electron-withdrawing substituents induce the production of more iodobenzene than substituted iodobenzene, whereas electron-releasing groups favor the formation of less iodobenzene than substituted iodobenzene; the other major products (diphenylmercury and symmetrically disubstituted diphenylmercury) arise via disproportionation of adsorbed phenylmercury radicals.At potentials corresponding to the second stage of reduction, electrolyses yield benzene, substituted benzene, and diorganomercury compounds; at potentials corresponding to the third stage of reduction, benzene and substituted benzene are formed.
- Mubarak, Mohammad S.,Peters, Dennis G.
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p. 673 - 677
(2007/10/02)
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- TRIORGANOTIN ARYL SELENIDES
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The Sn-Se bond in trimethyltin aryl selenides is cleaved on reaction with selenenyl halides, sulphenyl halides, alkyl halides and allyl halides.Thus Me3SnSePh reacts with PhSeCl, 4-Me-2-NO2C6H3SCl, RI (R = CH3 or Ph3SnCH2) and CH2=CHCH2Br to give PhSeSePh, 4-Me-2-NO2C6H3SSePh, RSePh and CH2=CHCH2SePh, respectively.The diselenide, PhSeSePh, is also obtained from Me3SnSePh on reaction with either 4-MeC6H4SO2Cl or NaIO4.Exchange reactions also occur between Me3SnSePh and Ph3SnCl or PhHgCl.
- Grant, Douglas W.,Wardell, James L.
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p. 161 - 166
(2007/10/02)
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- The Preparation of Some Manganese-Mercury Cluster Complexes and a Study of Their Redistribution Reactions
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The heterometallic cluster complexes (2), (3), and 2> (4) have been prepared by reaction of (1) with, respectively, HgPhCl, HgCl2, and Hg(CN)2.Some redistribution reactions of (2), (3), and (4) (in which the Hg atom is three- or four-co-ordinate) have been investigated and are compared with previously studied redistribution reactions of transition-metal-mercury complexes containing two-co-ordinate mercury atoms.
- Iggo, Jonathan A.,Mays, Martin J.
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p. 643 - 646
(2007/10/02)
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- MISE EN EVIDENCE EXPERIMENTALE DES HYDRURES RHgH
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The compounds RHgH have been characterised in methanol solution by their polarographic oxidation wave.Their decomposition and their action on RHgH products have also been studied.
- Devaud, Marguerite
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p. C27 - C29
(2007/10/02)
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- Metal Carbonyl Chemistry. Part 27. Formation of by Reaction of the Carbene Precursor Hg(CCl3)Ph with Octacarbonyldicobalt
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Octacarbonyldicobalt reacts with the dichlorocarbene precursor Hg(CCl3)Ph at 60 deg C in hexane to afford in 49percent yield.A similar complex is also obtained at 30 deg C, i.e. under conditions where appreciable thermal decomposition of Hg(CCl3)Ph to HgPhCl and CCl2 does not occur.Trapping expriments using cyclohexane have demonstrated that under both sets of conditions dichlorocarbene is formed.Possible mechanisms to explain the formation of the carbene and are discussed.
- Booth, Brian L.,Casey, Geoffrey C.,Haszeldine, Robert N.
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p. 403 - 406
(2007/10/02)
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- Mercury(II) and organomercury(II) complexes of thiols and dithiols, including british anti-lewisite
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The dithiols 2,3-dimercapto-1-propanol (British anti-Lewisite) and1,3-dimercapto-2propanol form complexes RHgS~SHgR (R = Me, Ph). The PhHg(II) complexes decompose in benzene and methanol at ambient temperature to form diphenylmercury. A 1:1 complex of Hg(II) with 1,3-dimercapto-2-propanol is dimeric in pyridine. Infrared, Raman, and 1H NMR spectra of RHg(II) and Hg(II) dithiol complexes are compared with those of PhHgSR (R = Me, Et, Pri, But, Ph, CH2CH2OH) and Hg(SR′)2 (R′ = Me, Et,But′, Ph, CH2CH2OH). Phenylmercury(II) thiolates have the coupling constant J(orthoH-199Hg) within the range 144-155 Hz. The complexes PhHgSR and Hg(SR″)2 (R″ = Et, But, Ph) are monomeric in chloroform; the chloroform insoluble complexes Hg(SR?)2 (R? = Me,CH2CH2OH) and organomercury(II) dithiolates are monomeric in pyridine. Aspects of the use of British anti-Lewisite as an antidote for mercury poisoning are discussed.
- Canty,Kishimoto
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p. 109 - 122
(2008/10/09)
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