- INFRARED, RAMAN AND FORCE FIELD STUDIES OF ETHYLMERCURY(II) HALIDES
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Vibrational assignments for Hg(C2H5)X (X=Cl, Br or I) and HgBr(C2D5) are proposed, on the basis of solution studies as far as possible.For the bromides, 21 force constants are refined in the presence of 12 constrained values from C2H5Cl and 12 of these ar
- Mink, J.,Goggin, P. L.
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- Organomercury Compounds. XXXI. Preparations and 199Hg N.M.R. Spectra of Organomercury Derivatives of 2-Phenylpyridine, Benzoquinoline, 1-Phenylpyrazole and 3,4,5-Trimethyl-1-phenylpyrazole, and the X-Ray Crystal Structure of Bismercury
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2-)Pyridin-2'-yl)phenylmercuric acetate has been prepared by mercuration of 2-phenylpyridine.Symmetrization of the corresponding chloride by alkaline sodium stannite gave bismercury, which was also prepared from 2-(2'-aminophenyl)pyridine by the diazo method and treatment of the initial product with copper powder and aqueous ammonia.Mercuration of benzoquinoline and 3,4,5-trimethyl-1-phenylpyrazole with mercuric acetate followed by treatment with lithium chloride yielded benzoquinolin-10-ylmercuric chloride and 2-(3',4',5'-trimethylpyrazol-1'-yl)phenylmercuric chloride respectively.Treatment of the former product with tribromide ions gave 10-bromobenzoquinoline.The exchange Grignard reaction between 1-phenylpyrazole and ethylmagnesium bromide to give 2-(pyrazol-1'-yl)phenylmagnesium bromide has been monitored by reactions with benzonitrile and D2O to establish optimum conditions for reaction with mercuric bromide giving bismercury.The 199Hg n.m.r. chemical shifts of the majority of mercurials are shifted substantially downfield to the corresponding simple phenylmercurials consistent with weak intramolecular coordination by the heterocyclic nitrogen donor atoms, but a small upfield shift is observed for bismercury.The X-ray crystal structure of bismercury 1/n, a 12.746(2), b 11.660(2), c 5.698(1) Angstroem, β 92.81(1) deg, V 845.8 Angstroem3> shows a centrosymmetric molecule with strong linear two coordination and significant but much weaker Hg-N interactions giving overall distorted square planar stereochemistry.The phenyl rings are mutually coplanar, whilst the two pyridin-2'-yl rings are parallel and inclined at 10.8 deg to the phenyl groups.
- Black, David St. C.,Deacon, Glen B.,Edwards, Gavin L.,Gatehouse, Bryan M.
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p. 1323 - 1336
(2007/10/02)
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- Oxidative addition reactions of compounds of the type (η5-C5Me5)Os(CO)LR (L = CO, PMe2Ph; R = alkyl). The role of oxidized intermediates in electrophilic cleavage reactions of osmium-carbon σ-bonds
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Compounds of the type Cp*Os(CO)LR (Cp* = η5-C6Me5; L = CO, PMe2Ph; R = Me, Et, i-Pr, CH2Ph), most of them new, have been prepared and their reactions with the electrophiles CF3CO2H, Br2, and HgBr2 have been investigated. All of the electrophiles oxidatively add to give labile, formally osmium(IV) complexes of the type [Cp*Os(CO)(L)(R)(E)]+X-, one of which, [Cp*Os(CO)(PMe2Ph)(Me)(HgBr)]+, has been isolated as the PF6- salt. In all cases, the osmium(IV) complexes decompose in solution to give the normal products of electrophilic cleavage.
- Johnston, Laura J.,Baird, Michael C.
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p. 2469 - 2475
(2008/10/08)
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- OXIDATIVE TRITYLDEMERCURATION OF ORGANOMERCURY COMPOUNDS
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In the reactions of Ph3CX (X=Cl, Br) with dialkylmercury compounds containing β-hydrogen atoms in the presence of oxygen the main result is determined by competition between two processes, i.e., β elimination (intermolecular hydride transfer) and oxidation with the formation of the peroxide Ph3COOAlk.By variation in the conditions of the reaction between dialkylmercury and triphenylbromomethane a method was found for the production of alkyl triphenylmethyl peroxides containing various primary and secondary alkyl radicals.The stereochemistry was investigated, and the mechanism of the formation of alkyl triphenylmethyl peroxides is discussed.
- Uglova, E. V.,Makhaev, V. D.,Reutov, O. A.
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p. 1386 - 1389
(2007/10/02)
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