Search

Tris(pentafluorophenyl)germanethiol, (C6F5)3GeSH (Ia), was obtained in good yield by heating the tris(pentafluorophenyl)germane with elemental sulphur or by the exchange between Et3GeSH and (C6F5)3GeBr. The reaction between sulphur and (C6F5)2GeH2 or C6F5GeH3 gives heterocyclic products with chains of alternating germanium and sulphur atoms in the cycles. The compounds [(C6F5)3Ge]2X (X = S, Se) were prepared by exchange reaction of (Et3Ge)2X with tris(pentafluorophenyl)germanium bromide and by reaction of chalcogens (S8, Se8) with hexakis(pentafluorophenyl)digermane. Ia reacts with diethylmercury affording (C6F5)3GeSHgEt. Insertion of elemental sulphur into the GeHg bond of bis[tris(pentafluorophenyl)germyl]mercury led to the thermally stable (C6F5)3GeSHgGe(C6F5)3.

Hexakis(pentafluorophenyl)digermane has a high reactivity that is not inherent to hexaphenyldigermane. The Ge−Ge bond in this compound is easily cleaved by water, methanol, ethylmercury chloride, and other compounds. The reactions proceed in either THF or acetone medium and fail to take place in nonpolar solvents.

Stepwise cleavage of carbonaluminum bonds was observed in the reaction of triethylsilanethiol, (C2H5)3SiSH, with triethylaluminum in hexane. Colourless crystalline associates [(C2H5)3SiSAI(C2H5)2]2, {[(C2H5)3SiS]2AlC2H5}1.4 or [(C2H5)3SiSAIS]x were formed respectively by the reaction of (C2H5)3Al with one, two or three moles of silanethiol. The first two complexes were found to be thermally unstable disproportionating into [C2H5AlS]x, [(C2H5)3Si]2S and (C2H5)3Al and [C2H5AlS]x and [(C2H5)3Si]2S, respectively. Triethylsilaneselenol and -tellurol react analogously with triethylaluminum, -gallium and -indium.

Tris(pentafluorophenyl)germanium bromide reacts with lithium aluminium hydride or triethylgermane to give tris(pentafluorophenyl)germane. On reaction with HgR 2 [where R = Et, Et 3 Ge and (Me 3 Si) 2 N] or reaction with diethylcadmium, the latter gave the hitherto unknown [(C 6 F 5 ) 3 Ge] 2 Hg or [(C 6 F 5 ) 3 Ge] 2 Cd. The germylmercurial compound could also be prepared by reaction of metallic mercury with [(C 6 F 5 ) 3 Ge] 2 Cd and by exchange of bis(triethylgermyl)mercury with (C 6 F 5 ) 3 GeBr. Some reactions of bis[tris(pentafluorophenyl)germyl]mercury are discussed.

1. Bis(triethylsilyl) selenide, bis(triethylsilyl) telluride, and their germanium analogs, react with mercury salts, HgX2 (X=Cl, CN), forming the mercury chalcogenide and the compound (C2H5)3MX (M=Si, Ge). 2. The reaction of [(C2H5)3Si]2Se with ethylmercury chloride gives triethylchlorosilane and bis(ethylmercury) selenide. 3. By reacting hydrochalcogenides of the series (C2H5)3SiXH (X=S, Se, Te) with bis(triethylgermyl)-mercury, using either a 1∶1 or a 1∶2 ratio, were respectively synthesized derivatives of the type (C2H5)3Si-XHgGe(C2H5)3 and [(C2H5)3SiX]2Hg.

The reaction of triethylaluminum with compounds of the (C2H5)3SiXH series (X=S, Se, Te) proceeds with a stepwise replacement of the ethyl groups by (C2H5)3SiX moieties. Depending on the ratio of the reactants, it is possible to obtain either the monosubstitution products (C2H5)3SiXAl(C2H5)2, or the disubstitution products [(C2H5)3SiX]2AlC2H5. The disproportionation reactions of these products were investigated.

Several complexes of bis[tri(pentafluorophenyl)germyl]eadmium with ligands of the donor type were synthesized.

1. The reaction of triethylsilylselenium hydride with triethylaluminum takes place with the formation of ethane and of heteroorganic compounds with an Si-Se-Al grouping as intermediate or final products. 2. The composition of the reaction products is determined by the ratio of the reactants and the temperature conditions.

Depending on the ratio of the reactants, the reaction of triethylsilylhydroselenide with diethylzinc and diethylcadmium proceeds with the formation of the mono- and disubstituted products of the series [(C2H5)3SiSe]nM(C2H5)2-n, where M=Zn, Cd; n=1 or 2, which were isolated as the crystalline associates.

1. It was shown that bis(triethylsilyl) sulfide and its isologs can be separated and studied by the GLC method. 2. The values of the specific retained volumes and the differential heats of solution (QS) of these compounds in a nonpolar solvent, and specifically in Apiezon L, were determined. It was found that QS is linearly dependent on the molecular weight of the compounds.