CS275928B6 - Tetracyanocomplex triphenylteluronium compounds and processes for their preparation - Google Patents

Abstract

The solution includes tetracyano complex triphenyltelluronium compounds of the general formula (I) [H 5 C 6 -Te(C 6 H 5 )-C 6 H 5 ] 2 . [ m (CN) 4 ] (I) where M is Zn 11 , Cd 11 . Hg 11. Their thermal decomposition up to 900 °C creates substances with the possibility of use as a semiconductor material and as a material for photocells. The method of their preparation consists in the fact that triphene 1 is treated with telluronium iodide in an aqueous medium on an aqueous suspension of the silver salt of the quanocomplex of the formula (II) Ag.[M(CN) 4 l where M has the above meaning.

Description

The invention relates to hitherto unknown triphenylteluronium tetracyanocomplexes of general formula (I)

[(C ₆ H ₅ ) ₃ Te ₂ ]. (I) wherein M is Zn, Cd, Hg.

Thermal decomposition of the cadmium-containing compound at a temperature of 900 to 1000 ° C produces cadmium telluride, which can be used as a semiconductor material, for photocells and solar cells. The tellurides can also be used in the production of thermocouples and photocells in radio electronics.

All prepared substances dissolve well in water, less in methanol and ethanol, do not dissolve in ether, acetone and chloroform with a melting point in the range of 100 to 320 ° C.

The process for the preparation of the compounds of formula I according to the invention is carried out by first preparing the silver salt of the corresponding cyanocomplex by adding an aqueous solution of silver nitrate to the aqueous solution of the potassium salt of the cyanocomplex at room temperature with vigorous stirring. The silver salt of the cyano complex is decanted with water and filtered off with suction on an S-4 frit. Then, a freshly prepared aqueous suspension of the silver salt of the cyanocomplex of formula (II) is prepared.

Ag ₂ [M (CN) ₄ ] (II) where M is as defined above, is treated with an aqueous solution of triphenyluronium iodide. The resulting silver iodide precipitate is separated from the filtrate on a 5-4 frit and the telluronium salt of the tetracyanocomplex remains in solution and the filtrate is slowly concentrated on an aqueous bath at 50-75 ° C to give the triphenylteluronium cyanocomplex.

Triphenylteluronium iodide of formula (III)

C ' ^C 6 ^H 5 can be prepared by reacting tellurium tetrachloride with phenylmagnesium bromide.

Example 1

Preparation of bis (triphenylteluronium) tetracyanocademate

To 2.94 g of potassium tetracyanocademate in 60 cm ^{3 of} water, 3.38 g of silver nitrate in 80 cm 3 of water are added with constant stirring for 40 minutes. The white precipitate of the silver salt of the cyano complex formed is decanted 5 times with 100 cm 3 of water.

To the suspension of the silver salt of the cyano complex thus prepared, 0.2 g of triphenylteluronium iodide in 400 cm 3 of warm water is added with constant stirring for 70 minutes. The resulting rye microcrystalline precipitate is filtered off with suction on an S-4 frit and the tellurium salt of the cyano complex remains in the light yellow solution. The filtrate is concentrated in a water bath to crystallize at 60-75 ° C. A product with an yield of 80 «is formed.

Repeated crystallization from aqueous-chloroform solution on several occasions gave white flakes of bis (triphenylteluronium) tetracyanocademate with a melting point of 105 ° C. For N ₄ Te ₂ Cd (934.29) calculated 51.42% C, 3.23% H, 5.11% N, 27.31% Te, 12.03% Cd, found 51.03% C, 3 , 1) 5 H, 5.10% N, 27.19% Te, 12.02% Cd.

Example 2

Preparation of bis (triphenylteluronium) tetracyanosinate

To an aqueous solution of 2.38 g of potassium tetracyanosinate in 50 cm ^{3 of} water with constant stirring for 30 minutes is added an aqueous solution of 3.38 g of silver nitrate in 80 cm ^{3 of} water. The white precipitate is decanted 4 times with 150 cm ^{3 of} water and filtered off on an S-4 frit.

To a freshly prepared aqueous suspension of 3.38 g of the silver salt of potassium tetracyanosinate is added a warm aqueous solution of 0.35 g of triphenylturonium iodide soluble in 450 cm ³ at 50 ° C. After stirring for 20 minutes, the rye precipitate separated. The colorless filtrate was concentrated to crystallize at 65 ° C. A product with a yield of 75 S is formed. Crystallization several times from aqueous solution gave white needles of the desired product with a melting point of 320 ° C.

For Ο ^ θΗ ^ θΝ ^ Τβ ^ η (884.26) calculated: 54.33% C, 3.41 Si H, 6.33% N, 28.52% 7.39% Zn :, found: 54, 03% C, 3.22% H, 5.32% N, 24.70% Te, 19.01% Hg.

Te,

Example 3

Preparation of tetracyanoortuthatanate bis (triphenyluronium)

The reaction of a saturated aqueous solution of 3.82 g of potassium tetracyanoortuate and an aqueous solution of 3.38 g of silver nitrate gave a white precipitate for 15 minutes with stirring at room temperature. After decanting the precipitate 5 times with 100 cm ^{3 of} water, the precipitate is filtered off on an S-4 frit.

To the thus prepared aqueous suspension of the silver salt of the cyanocomplex is added 0.30 g of triphenylteluronium iodide dissolved in 400 cm ^{3 of} water at 55 ° C. The precipitate formed is filtered off with suction. The filtrate is concentrated to crystallize at 60 ° C.

Crystallization several times from water gives a white product. Yield of reaction 58

For ^ε ήΟ ^Η 2ΟΝ _or Τβ ₂ ς (1019.47) calculated: 47.12% C, 2.96% H, 5.49 XN, 24.73% Te, 19.67% Hg; found 46.97% C, 2.85% H, 5.32% N, 24.70% Te, 19.01% Hg.

Claims (2)

3 CS 275928 B6 i, PATENT'S CLAIMS A triphenylteluronium tetracyanocomplex compound having the formula (I) C 6 H 5 H 5 C 6 Te [mCl 2] 4] (I) C 6 H 5 wherein M is Zn 11, Cd 11, Hg 11. 2. A process for the preparation of compounds of formula (I) according to claim 1, characterized in that Ag2 M (CN) 4 (II) wherein M has the meanings given above is substituted by triphenylteluronium iodide in an aqueous medium at a water phase of vigorous stirring, wherein the silver iodide precipitate is filtered off and the aqueous solution containing the tetra-cyano complex of triphenylteluronium is concentrated to crystallize.