Organomercury compounds. XXII. Syntheses of polybromophenylmercurials by decarboxylation reactions

1977 ◽  
Vol 30 (5) ◽  
pp. 1013 ◽  
Author(s):  
GB Deacon ◽  
GJ Farquharson ◽  
JM Miller
Keyword(s):  
Thermal Decomposition ◽  
Sodium Chloride ◽  
Mass Spectra ◽  
Mercuric Acetate ◽  
Similar Treatment ◽  
Phenylmercuric Acetate ◽  
Pyridine Complexes ◽  
Organomercury Compounds ◽  
Mercuric Halides

The mercuric polybromobenzoates, (C6Br2CO2)2Hg, (XC6Br4CO2)2Hg (X = p-F, p-Cl, p-Me, o-Me, p-MeO or m-MeO) and (2,6-Me2C6Br3CO2)2Hg, and phenylmercuric pentabromobenzoate have been prepared by reaction of mercuric acetate or phenylmercuric acetate with the appropriate polybromobenzoic acids. Thermal decomposition of (C6Br5CO2)2Hg, (XC6Br4CO2)2Hg, (X = p-F, p-Cl or p-MeO) and C6Br5C02HgPh in boiling pyridine gave the new polybromophenylmercurials (C6Br&Hg, (XC6Br4)2Hg and C6Br5HgPh respectively, but similar treatment of (XC6Br4C02)2Hg (X = p-Me, o-Me or m-MeO) and (2,6-Me2C6Br3C02)2Hg yielded pyridine complexes of the mercuric carboxylates. Mercuric p-methyltetrabromobenzoate underwent decarboxylation in boiling nitrobenzenelpyridine giving (p-MeC6Br4),Hg, but the method could not be extended to (0-Mec~Br~C0~)o~r H(2g,6 -Me2C6Br,C02)2Hg. Decarboxylation of XC6Br4C02H (X = o-Me or m-MeO) was effected in molten mercuric trifluoroacetate giving, after treatment of the products with sodium chloride, the corresponding tetrabromophenylmercuric chlorides. All mercurials underwent cleavage with iodine or triiodide ions in hot dimethylformamide to give the corresponding iodopolybromobenzenes, and (C6Br5)2Hg was converted into C6Br5HgX (X = C1 or Br) by the corresponding mercuric halides in hot xylene/nitrobenzene. Thermal symmetrization of C6Br5HgX (X = C1, Br, or Ph) is detectable prior to melting, but (C6Br5),Hg is stable to at least 400'. The mass spectra of the polybromophenylmercurials are discussed.

Organomercury Compounds. XVI. Thermal decomposition reactions of mercuric arenesulphonate dihydrates

1973 ◽  
Vol 26 (3) ◽  
pp. 541 ◽  
Author(s):  
PG Cookson ◽  
GB Deacon
Keyword(s):  
Thermal Decomposition ◽  
Acetic Acid ◽  
Sulphuric Acid ◽  
Mercuric Acetate ◽  
Sodium Salts ◽  
Decomposition Reactions ◽  
Tetraphenylarsonium Chloride ◽  
Organomercury Compounds ◽  
Sulphur Trioxide

Thermal decomposition of the mercuric arenesulphonate dihydrates Hg(03SR)2,- 2H20 (R = C6X5, p-HC6X4, or m-HC6C14; X = C1 or F) at c. 130-240" gave the corresponding diarylmercurials, the polyhalogenobenzenes RH, and sulphur trioxide (or sulphuric acid) in all cases, together with RS03H (R = C6F5 or p-HC6F4), and p-(p-HC6F4S03Hg),C6F4. By contrast, decomposition of Hg(03SR)2,2H20 (R = m-HC6F4 or o-HC6X4) gave the corresponding (-HgC6X4S03-), derivatives, sulphonic acids, polyhalogenobenzenes, and sulphur trioxide in all cases, together with m-HC6F4HgO3S-m-HC6F4 and o-(o-HC~C~~SOJH~),C~C~~. The compounds RHg03SR (R = C6C15, isolated as the monopyridinate, or p-HC6C14) were obtained from decomposition of the appropriate mercuric sulphonates at c. 165'. Identities of (-HgC6X4S03-), derivatives were established mainly by cleavage with triiodide ions in N,N-dimethylformamide giving the salts M(IC6X,S03) (M = Na or S-benzylthiouron- ium), and of (HC6X4S03Hg)2C6X4 derivatives by similar degradation giving 12C6X4 and M(HC6X4S03) (M = Na or Ph4As). Similar degradation of C6C15Hg03SC6C15,py, p-HC6Cl,Hg03S-p-HC6C14, and the known mercurials C6C15HgCl, (p-HC6C14),Hg, and (0-HC6C14),Hg gave the corresponding iodopolychlorobenzenes. The mercurated derivative (-o-H~C,F~SO~-)~ gave (-0-HgCsF4-)3 on thermal decomposition, and crystallization from water yielded ( - o - H ~ C ~ F ~ S ~ ~ - ) , , ~ ~ H ~ ~ , which was converted into (Ph4As)(o-C1HgC6F4S03) by tetraphenylarsonium chloride. The mercuric sulphonates were prepared from mercuric acetate and the appro- priate sulphonic acids in acetic acid (X = C1) or water (X = F). Sulphonic acids, obtained by sulphonation reactions, were characterized as the dihydrates and in some cases sodium salts (polychloro derivatives) or as barium and tetraphenylarsonium salts (tetrafluoro derivatives).

Metal Complexes with Tetrapyrrole Ligands, XLV. The Mercuration of Nickel(II), Palladium(II), and Platinum(II) Porphyrins

1987 ◽  
Vol 42 (8) ◽  
pp. 1003-1008 ◽  
Author(s):  
Johann W. Buchler ◽  
Gerhard Herget
Keyword(s):  
Sodium Chloride ◽  
Metal Complexes ◽  
Negative Charge ◽  
Mercuric Acetate ◽  
Reaction Times ◽  
Total Density ◽  
Electrophilic Attack ◽  
Aqueous Sodium ◽  
Porphyrin Ligand ◽  
Rapid Reaction

AbstractThe mercuration of 5,10,15,20-tetrakis(4-methylphenyl)porphyrin complexes M(TTP)** (2a-c; M = Ni, Pd, Pt) is described. Treatment of Ni(TTP) (2a) with mercuric acetate in refluxing benzene and subsequently with aqueous sodium chloride yields a mixture of species M(TTP-HgnIn) (1 < n < 3) from which the monomercurial, Ni(TTP-HgCl) (3a) is isolated in 35% yield after silica chromatography. A more rapid reaction occurs with mercuric trifluoroacetate in chlorobenzene. With this system, Pd(TTP-HgCl) (3b) and Pt(TTP-HgCl) (3c) along with their bis-, tris-, and tetrakis-mercurated analogs are obtained. The reaction times indicate that replacement of NiII by PdII and PtII progressively diminishes the rate of electrophilic attack at the porphyrin periphery, consistent with a decrease of the total density of negative charge on the porphyrin ligand in these complexes.

Organomercury compounds. XIV. The preparations of bispolychlorophenylmercury compounds by mercuration reactions

1972 ◽  
Vol 25 (8) ◽  
pp. 1645 ◽  
Author(s):  
RJ Bertino ◽  
GB Deacon ◽  
FB Taylor
Keyword(s):  
Thermal Decomposition ◽  
Elevated Temperatures ◽  
Organomercury Compounds

The bispolychlorophenylmercurials R2Hg (R = C6Cl5 2,3,4,5-Cl4H, 2,3,4,6- Cl4C6H 2,3,5,6-C14C6H, 2,3,4-Cl3C6H2, 2,4,6-Cl2C6H2, and 2,5-Cl2C6H3) have been prepared by direct mercuration of pentachlorobenzene, 1,2,3,4-tetrachlorobenzene, 1,2,3,5-tetrachlorobenzene, 1,2,4,5-tetraohlorobenzene, 1,2,3-trichlorobenzene, 1,3,5-trichlorobenzene, and 1,4-dichlorobenzene respectively, with mercuric trifluoroacetate at elevated temperatures. Similar syntheses of bispentachlorophenylmercury from mercuric difluoroacetate and fluoroacetate have also been carried out. From merouration of pentaohlorobenzene with mercuric trifluoroaoetate and difluoroacetate under milder conditions, pentachlorophenylmercuric trifluoroacetate and difluoroacetate have been obtained. The former undergoes thermal decomposition into bispenta chlorophenylmercury and mercuric trifluoroacetate.

Organomercury compounds. VII. Complexes of arylmercuric halides with bidentate ligands

1968 ◽  
Vol 21 (7) ◽  
pp. 1757 ◽  
Author(s):  
AJ Canty ◽  
GB Deacon
Keyword(s):  
Organometallic Compounds ◽  
Bidentate Ligand ◽  
Chemistry Department ◽  
Bidentate Ligands ◽  
Solution Studies ◽  
Unknown Structure ◽  
Organomercury Compounds ◽  
Neutral Ligands ◽  
Mercuric Halides ◽  
Low Solubility

The complexes, C6F5HgXL2 [X = Br or C1; L2 = 2,2'-bipyridyl (bipy), 1,l0-phenanthroline (phen), 3,4,7,8-tetramethyl-1,l0-phenanthroline (tmp), or 2,9-dimethyl-1,l0-phenanthroline (dmp)], C6Cl5HgClL2 (L, = phen, tmp, or dmp), and PhHgClL2 (L2 = phen or tmp), have been prepared, but attempts to prepare PhHgCl bipy or complexes of phenylmercuric bromide were unsuccessful. Evidence that the complexes contain four coordinate mercury has been obtained from infrared spectroscopy. All complexes, except C6Cl5HgCl phen, C6Cl5HgCl dmp, and PhHgCl tmp, undergo complete or partial disproportionation reactions, 2RHgXL2 → L2HgX2 +R2HgL2 (or R2Hg + L2), in boiling benzene. Although disproportionation or low solubility precludes solution studies on the majority of the derivatives, it has been shown that C6F5HgX dmp complexes are monomeric in acetone and that PhHgCl phen undergoes dissociation, PhHgCl phen + PhHgCl + phen, in this solvent. Four-coordinate complexes of mercuric halides with neutral ligands, L,HgX, (L = a neutral unidentate or L, = a neutral bidentate ligand; X = C1, Br, or I), are well kno~n,l-~ but analogous complexes of organomercuric halides, viz. RHgXL,, were unknown prior to this investigation. Reactions of organomercuric halides with ligands generally result in disproportionation, the corresponding diorganomercurial and mercuric halide complex being f~rmed.~-~ In some cases intermediate complexes RHgL+X- have been i~olated~,~ or detected in soluti~n,~-~~ and a 1 : 1 complex of unknown structure between pyridine and cis-2- * Part VI, J. organomet. Chem., in press. Preliminary communications for Part VII: Canty, A. J., Deacon, G. B., and Felder, P. W., Inorg. nzlcl. Chem. Lett., 1967,3,263; Deacon, G. B., and Canty, A. J., Inorg. %ucl. Chem. Lett., 1968, 4, 128. t Chemistry Department, Monash University, Clayton, Vie. 3168. Evans, R. C., Mann, F. G., Peiser, H. S., and Purdie, D., J. chem. Soc., 1940, 1209. Cass, R. C., Coates, G. E., and Hayter, R. G., J. chem. Soc., 1955, 4007. Coates, G. E., and Ridley, D., J. chem. Soc., 1964, 166. Coates, G. E. "Organometallic Compounds." 2nd. Edn, pp. 78-82. (Methuen: London 1960.) Seyferth, D., and Towe, R. H., Inorg. Chem., 1962, 1, 185. Coates, G. E., and Lauder, A., J. chem. Soc., 1965, 1857. Brodersen, K., Chem. Ber., 1957, 90, 2703. Schwarzenbach, G., and Schellenberg, &I., Helv. chim. Acta, 1965, 48, 28. Goggin, P. L., and Woodward, L. A., Trans. Faraday Soc., 1962, 58, 1495. Dessy, R. E., Budde, W. L., and Woodruff, C., J. Am. chem. Soc., 1962, 84, 1172. Aust. J. Chem., 1968, 21, 1757-67

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