100-56-1Relevant articles and documents
Chiral organotin hydrides containing intramolecular coordinating substituents
Dakternieks, Dainis,Dunn, Kerri,Schiesser, Carl H.,Tiekink, Edward R.T.
, p. 209 - 220 (2000)
A series of chiral non-racemic triorganotin halides and triorganotin hydrides containing one or two (1R,2S,5R)-menthyl (Men) substituents as well as the 8-dimethylaminonaphthyl (L) or 2-[(1S)-1-dimethylaminoethyl]phenyl (L*) substituents has been synthesised and characterised. Each of the compounds MenPhLSnBr (1) and MenPhLSnH (2) has a stereogenic tin centre and the compounds were isolated in diastereomeric ratios of 60:40 and 66:33, respectively. Compounds MenPhL*SnCl (3) and MenPhL*SnH (4) were synthesised with diastereomeric ratios of 73:27 and 64:36, respectively. Single crystal X-ray analysis of MenPhL*SnCl (3), Men2L*SnCl (8), and MenPh2LSn (10) reveals that each structure has a tendency towards penta-coordination at the tin centre as a result of intramolecular N→Sn interactions. AM1 calculations successfully predict the molecular geometries observed in the solid state as well as the diastereomeric ratios observed in solution.
Organotin compounds X. Organotin hydride addition to methyl cyclohexene-1-carboxylate and methyl indene-3-carboxylate
Ayala, A. D.,Giagante, N.,Podesta, J. C.,Neumann, W. P.
, p. 317 - 330 (1988)
Free radical hydrostannation of methyl cyclohexene-1-carboxylate (I) and methyl indene-3-carboxylate (III) with trialkyltin hydrides, R3SnH (R=Me, n-Bu, Ph) gives the energetically unfavourable cis products, 2-trialkylstannyl cyclohexanecarboxylate (II) 2-trialkylstannyl indene-1-carboxylate (IV) in high yields, via a trans addition of the thin hydrides.The hydride abstractions by the intermediate trialkylstannylcyclohexanyl (VIII) and trialkylstannylindanyl (IX) intermediate radicals take place stereospecifically, and exclusively from the less hindered ring side.The structures of the isomers II and IV were established by (a) their transformation into the corresponding chlorodialkylstannylderivatives V and VI, which were shown spectroscopically to have cis stereochemistries by intramolecular complexation of the ester group, and (b) their NMR data.Full 1H, 13C, and 119Sn NMR data are given.
Phenylmercury chloride: Its single-crystal X-ray structure and some aspects of its biological chemistry
Wilhelm, Michaela,Saak, Wolfgang,Strasdeit, Henry
, p. 35 - 38 (2000)
A single crystal of phenylmercury chloride (PhHgCl) was obtained by serendipity from a solution of diphenylmercury (HgPh2) and dihydrolipoic acid in tetrahydrofuran / carbon tetrachloride. The crystal structure of PhHgCl is pseudotetragonal. It is best described in the orthorhombic space group Cmma with a = 6.856(1), b = 6.882(1), c = 14.309(2) A (at 193 K), and Z = 4. The Cl-Hg-C moiety of the PhHgCl molecule is exactly linear. The bond lengths at the Hg atom are Hg-Cl 2.345(2) and Hg-C 2.044(9) A. In the crystal, the molecules are arranged in double layers parallel to the a,b plane. In a model medium for the gastric juice (0.1 M DCl in D2O / [D8]dioxan, 37 °C), HgPh2 reacts to form PhHgCl. HgCl2, which would result from complete dearylation, cannot be isolated from the reaction mixture. However, it appears that a small equilibrium concentration of HgCl2 may be present, because on addition of 1,4,7-trithiacyclononane (ttcn) and diethyl ether, the dichloride can be trapped as solid [Hg(ttcn)2][HgCl4]. We estimate that after oral uptake of HgPh2 20 - 90% are transformed into PhHgCl in the stomach after 30 min.
DIRECT TRANSFER OF ALIPHATIC AND AROMATIC SUBSTITUENTS FROM ORGANOSILATRANES TO MERCURY(II) SPECIES
Nies, J. Dirk,Bellama, Jon M.,Ben-Zvi, Nava
, p. 315 - 320 (1985)
The relative reaction rates of several silatranes (derivatives of 2,8,9-trioxa-5-aza-1-silatricyclo1,5>undecane) and HgCl2 in acetone-d6 to yield the corresponding organomercury compound are of the order of e.g., 5 * 10-1 1 mol-1 sec-1 or slightly less, a rate that is unexpectedly high compared to the essentially inert parent organotrialkoxysilanes.Thus, the apical Si-C bond of the silatrane is extraordinarily susceptible to direct electrophilic attack by mercury(II).The rates decrease in the order CH2=CH, C6H5, p-ClC6H4 > CH3 > CH3CH2, CH3CH2CH2 > C6H11, ClCH2, Cl2CH, CH3CH2O.The effects of varying the solvent and the counterions are noted, and the probable mechanism is discussed.
Metal Carbonyl Chemistry. Part 27. Formation of by Reaction of the Carbene Precursor Hg(CCl3)Ph with Octacarbonyldicobalt
Booth, Brian L.,Casey, Geoffrey C.,Haszeldine, Robert N.
, p. 403 - 406 (1980)
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.
Synthesis of [2-[(dimethylamino)methyl] phenyl-C1N]-(phenyl) gold(III) complexes. Crystal structure of two modifications of chloro[2-[(dimethylamino)methyl]-phenyl-C1N](phenyl)gold(III)
Vicente, Jose,Chicote, M.Teresa,Bermudez, M.Dolores,Sanchez-Santano, Maria J.,Jones, Peter G.
, p. 381 - 390 (1988)
The reaction ( 1 1) between [Au(2-C6H4CH2NMe2)Cl2] and [HgPh2] gives [Au(2-C6H4CH2NMe2)(Ph)Cl]. From this complex, the neutral [Au(2-C6H4CH2NMe2)(Ph)X] (X : Br, I, CN, MeCO2) complexes are obtained by reaction with X- salts. Cationic complexes [Au(2-C6H4CH2NMe2)(Ph)L]ClO4 (L : pyridine, tetrahydrothiophene) are obtained by treatment of [Au(2-C6H4CH2-NMe2)(Ph)Cl] with ClO4- and the relevant ligand L. The complex [Au(2-C6H4-CH2NMe2)(Ph)Cl] crystallizes in two modifications, both with three independent molecules in the asymmetric unit. The AuN and AuCl bonds are long, consistent with the appreciable trans influence of the C-donor ligands. The molecules differ somewhat in the orientation of the rings.
THE REACTIONS OF PHENYL(B-CARBORANYL)IODONIUM SALTS WITH NUCLEOPHILES
Grushin, V. V.,Shcherbina, T. M.,Tolstaya, T. P.
, p. 105 - 118 (1985)
The reactions of phenyl(9-o-carboranyl)-, phenyl(9-m-carboranyl)- and phenyl(2-p-carboranyl)-iodonium salts with the nucleophiles F-, Cl-, Br-, OH-, C5H5N, Hg and CN- were studied.Depending on the nature of the nucleophile and the carborane ligand in each iodonium compound, these reactions either proceed as nucleophilic substitution or via a radical mechanism.Nucleophilic substitution, which takes place at the boron atom, of the carborane nucleus only, gives carboranylation products of nucleophiles.Free-radical processes are characterized by braking of the C-I+ bonds with the formation of phenyl radicals and their transformation products.The reasons for such an unusual behaviour of phenyl(B-carboranyl)iodonium salts in reactions with nucleophilic agents are discussed in the light of the results obtained and previous results.
Organostannanes Derived from (-)-Menthol: Controlling Stereochemistry during the Preparation of (1R,2S,5R)-Menthyldiphenyltin Hydride and Bis((1R,2S,5R)-menthyl)phenyltin Hydride
Dakternieks, Dainis,Dunn, Kerri,Henry, David J.,Schiesser, Carl H.,Tiekink, Edward R. T.
, p. 3342 - 3347 (1999)
Reaction of (1R,2S,5R)-menthylmagnesium chloride (MenMgCl) with triphenyltin chloride in THF proceeds with epimerization of the C-1 carbon of the menthyl group and results in a mixture of (1R,2S,5R)-menthyltriphenyltin (1) and (1S,2S,5R)-menthyltriphenyltin (2). Addition of Lewis bases such as triphenylphosphine to the THF solution of triphenyltin chloride prior to addition of the Grignard reagent suppresses epimerization and enables isolation of pure 1. An epimerization mechanism involving one-electron-transfer reactions is postulated. Compound 1 is the precursor for reactions that lead to the formation of a series of compounds, namely, (1S,2S,5R)-menthyldiphenyltin iodide (4), (1S,2S,5R)-menthyldiphenyltin fluoride (5), (1S,2S,5R)-menthyldiphenyltin hydride (6), (1S,2S,5R)-menthylphenyltin dibromide (7), and (1S,2S,5R)-menthylphenyltin dichloride (8). The synthesis of the dimenthyl derivatives bis((1S,2S,5R)-menthyl)diphenyltin (9), bis((1S,2S,5R)-menthyl)-phenyltin iodide (10), bis((1S,2S,5R)-menthyl)phenyltin hydride (11), and bis((1S,2S,5R)-menthyl)tin di(chloroacetate) (12) is described. Crystal structure determinations of 7,8, and 12 confirm the absolute configuration of the menthyl groups.
Organotin compounds. XI. Organotin hydride additions to various methyl dihydronaphthalenecarboxylates
Podesta, Julio C.,Ayala, Alicia D.,Chopa, Alicia B.,Giagante, Nelda N.
, p. 39 - 56 (1989)
Free rdical hydrostannation of methyl 3,4-dihydronaphthalene-1-carboxylate (I), methyl 3,4-dihydronaphthalene-2-carboxylate (III), and methyl 1,4-dihydronaphthalene-2-carboxylate (V) with triorganotin hydrides, R3SnH (R = Me, n-Bu, Ph) gives the energetically unfavourable cis products, 2-triorganostannyl-1,2,3,4-tetrahydronaphthalene-1-carboxylate (II), 1-triorganostannyl-1,2,3,4-tetrahydronaphthalene-2-carboxylate (IV), and 3-triorganostannyl-1,2,3,4-tetrahydronaphthalene-2-carboxylate (VI) in high yields, via a trans addition of the tin hydrides.The hydride abstractions by the intermediate 2-, 1- and 3-triorganostannyl-1,2,3,4-tetrahydronaphthyl radicals (XI, XII and XIII respectively) take place stereospecifically and exclusively from the less-hindered ring side.The structures of the isomers II, IV, and VI, were established by (a) their transformation into the corresponding chlorodiorganostannyl derivatives VIII, IX, and X, which were shown spectroscopically to have cis stereochemistries by intramolecular complexation of the ester group, and (b) their NMR data.Full 1H, 13C, and 119Sn NMR data are given.
AROMATIC SUBSTITUTION. THE EFFECT OF ALCOHOLIC SOLVENTS ON THE REACTION OF PHENYLTRIETHYLTIN WITH MERCURY(II) SALTS
Sedaghat-Herati, Mohammad Reza,Nahid, Parvin
, p. 307 - 312 (1982)
Second-order rate constants are reported for the cleavage of the phenyl-tin bond of phenyltriethyltin by mercury(II) salts in ethanol, propan-1-ol, propan-2-ol and butan-1-ol.It is shown that the reactivity order for the mercury(II) salts is HgI3-/s
