2179-81-9Relevant academic research and scientific papers
Reaction of [SNS][AsF6] with Hg(CN)2 and PhHgCN: Preparation and crystal structures of [Hg(CNSNS)2][AsF6]2 and [PhS4N3Ph][AsF6]
Aherne, Christine M.,Banister, Arthur J.,Lavender, Ian,Lawrence, Simon E.,Rawson, Jeremy M.,Clegg, William
, p. 1877 - 1886 (1996)
Reaction of Hg(CN)2 with two equivalents of the salt [SNS][AsF6] provided a high yield (92%) route to the first metallo-dithiadiazolylium salt, [Hg(CNSNS)2][AsF6]2(I). Its structure and reactivity are compared with those of the analogous organic derivatives, [R.CNSNS][AsF6]; I initiates the polymerization of tetrahydrofuran and undergoes metathesis reactions but reduction leads to decomposition (forming S4N4), whilst oxidation with the halogens provides a novel route to the salts [X.CNSNS][AsF6] (X = Cl, Br and I). In contrast, reaction of PhHgCN with [SNS][AsF6] yielded the sulfur-nitrogen chain compound, [PhS4N3Ph][AsF6] (II) with a cation consisting of an alternating S/N chain strung between two phenyl groups.
Nucleophilic cleavage of the Si-C bond in organotrifluorosilanes and diorganodifluorosilanes
Voronkov, M. G.,Chermov, N. F.,Perlova, E. M.
, p. 225 - 230 (2007/10/02)
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.
NMR INVESTIGATION OF ARYL- AND BENZYL-MERCURIC COMPOUNDS; EXPERIMENTAL EVIDENCE FOR ?-? CONJUGATION INVOLVING THE CARBON-MERCURY BOND
Michel, Elie,Perie, Jacques,Lattes, Armand
, p. 1 - 12 (2007/10/02)
199Hg and 13C NMR spectra of a large number of aryl- and benzyl-mercuric compounds (ArHgX and ArCH2HgX) have been obtained, in order to throw more light on the relationship between the coordination state of the mercury atom and its NMR parameters.For the aryl series ArHgCl there is a good correlation between the 199Hg chemical shift and ?+, with electron releasing substituents in Ar resulting in an upfield chemical shift.This correlation arises from the contribution of the paramagnetic term to the chemical shift.Comparison of the NMR parameters in ArHgCl and ArCH2HgCl provides unambiguous evidence for conjugation between the C-Hg bond in ArCH2HgCl and the aromatic ring, the C-Hg system behaving as a strongly donating group.This is explained in terms of vertical stabilization, as proposed by Traylor.
