2097-72-5Relevant academic research and scientific papers
Facile syntheses of homoleptic diarylmercurials via arylboronic acids
Partyka, David V.,Gray, Thomas G.
, p. 213 - 218 (2009/04/13)
A general procedure for the syntheses of diarylmercurials is presented. Reactions proceeded in isopropanol in the presence of a base and arylboronic acid. With one exception, all reactions proceeded in good to excellent yields, and this procedure was appl
Symmetrization of phenylmercuric hydroxides by the action of nickel(II) and cobalt(II) acetylacetonates. Isolation and structural characterization of an intermediate in this reaction
D?ring, Manfred,Hahn, Gabriela,Stoll, Michael,Wolski, Alexander C.
, p. 1879 - 1883 (2008/10/08)
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.
Electrochemical Reduction of 4-Iodo- and 4-Bromoanisole at Mercury and Carbon Cathodes in Dimethylformamide
Mubarak, Mohammad S.,Karras, Louis L.,Murcia, Noel S.,Bart, John C.,Stemple, Joseph Z.,Peters, Dennis G.
, p. 1065 - 1070 (2007/10/02)
In dimethylformamide containing tetramethylammonium perchlorate, cyclic voltammograms for reduction of 4-iodo- and 4-bromoanisole at mercury and carbon electrodes exhibit single irreversible waves corresponding formally to two-electron cleavage of the carbon-halogen bond.In preparative-scale controlled-potential electrolyses of 4-iodoanisol at mercury pool cathodes, a two-to-one mixture of anisole and bis(p-anisyl)mercury is obtained at potentials close to the peak potential, whereas anisole is the only species formed at more negative potentials.Reduction of 4-iodoanisole at mercury appears to proceed via p-anisyl radicals that (i) yields adsorbed p-anisylmercury radicals which disproportionate to give bis(p-anisyl)mercury or (ii) undergo further reduction, followed by protonation, to afford anisole.Electrolyses of 4-iodoanisole at carbon electrodes, as well as reduction of 4-bromoanisole at both mercury and carbon, result solely in the production of anisole; presumably, even if p-anisyl radicals are generated transiently, they undergo facile reduction to p-anisyl carbanions, which are protonated immediately to yield anisole.
Synthesis and Interconversion of, and Restricted Rotation in, Phenyl Complexes of Ruthenium(II)
Probitts, E. Jane,Saunders, David R.,Stone, Michael H.,Mawby, Roger J.
, p. 1167 - 1174 (2007/10/02)
The preparation and characterization of a range of phenyl complexes of ruthenium(II) are reported.For many of the complexes there is a substantial barrier to rotation of the phenyl ligand about the metal-phenyl bond, and n.m.r. studies have shown how the rate of rotation is affected by changes in the ligands in the complexes.Reaction of complexes with phosphorus or arsenic ligands L provides a convenient route to : 31P and 13C n.m.r. studies have demonstrated the sequence of steps involved and the stereochemistry of the intermediates, showing the influence of the trans-labilizing and trans-directing effects of the phenyl ligand.
Electrochemical Reduction of Unsymmetrically Substituted Diphenyliodonium Salts at Mercury Cathodes in Dimethylformamide
Mubarak, Mohammad S.,Peters, Dennis G.
, p. 673 - 677 (2007/10/02)
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.
Dialkyl, Diaryl, and Alkyl Aryl Complexes of Ruthenium(II)
Saunders, David R.,Stephenson, Martin,Mawby, Roger J.
, p. 2473 - 2478 (2007/10/02)
Whereas HgR2 (R=methyl or aryl) converts trans-(Ru(CO)2Cl2(PMe2Ph)2) exclusively into (Ru(CO)2R(Cl)(PMe2Ph)2) and does not react with cis-(Ru(CO)2Cl2(PMe2Ph)2), LiR reacts with either isomer to yield (Ru(CO)2R2(PMe2Ph)2) and also catalyses conversion of the trans isomer into the cis.The initial attack by R- is belived to be on a carbonyl ligand.Treatment of (Ru(CO)2R(Cl)(PMe2Ph)2) with LiR' yields mixed complexes (Ru(CO)2R(R')(PMe2Ph)2).In all cases the two organic ligands are mutually cis.The dimethyl complex undergoes reversible carbonylation to form mono- and di-acetyl complexes, and (Ru(CO)2Me(Ph)(PMe2Ph)2) also forms an acetyl coplex, but aryl ligands are unaffected by treatment with CO.
