Organozinnverbindungen mit raumfüllenden Arylgruppen, II

Abstract

Eine Gegenuberstellung der charakteristischen Kristallformen der Isomeren I, I1 und 111 zeigen die Mikroaufnahmen der Abbildungen 2, 3 und 4 : Abbildd. 2-4. Kristallformen der Verbindungen 1-111 Abbild. 2. Tetrakis-bi-Abbild. 3. Tetrakis-bi-Abbild. 4. Tetrakis-biphenylyl-(2)-zinn (I) ; phenylyl-(3)-zinn (11); phenylyl-(4)-zinn (111) ; ca. 30fach, aus Essigester ca. 60fach, aus o-Dichlorbenzol ca. 30fach, aus Essigester GERHARD BXHR und ROLF GELIUS Organozinnverbindungen mit raumfiillenden Arylgruppen, IlReindarstellung und Eigenschaften von Te1ru-phenunthryZ-(9)-zinn (I), Tetranaphrhyl-(l)-zinn (11) und Tefrurnesityl-zinn (111) werden mitgeteilt.Wie kiirzlich am Beispiel des Tetrakis-biphenylyl-(2)-zinns gefunden wurdel), entstehen Zinntetraaryle mit raumfiillenden Arylgruppen mitunter unerwartet glatt, doch bereitet die Reindarstellung solcher Verbindungen Schwierigkeiten. Infolge ihrer sehr geringen Loslichkeit in fast allen Medien und dem oft ganz ahnlichen Loslichkeitsverhalten hartnackig festgehaltener Beiprodukte bringen Reinigungsoperationen erhebliche Substanzverluste mit sich. Zudem kommen Reinheitskontrollen durch Schmelzpunktsbestimmungen nicht in Betracht, weil die Verbindungen trotz auffallend hoher Thermostabilitat vor dem Schmelzen ZerfaU erleiden, dessen schleichender Eintritt von schwer reproduzierbaren Umstanden (Aufheizgeschwindigkeit, wohl auch katalytischen Einflussen u. a.) abhiingt. Aus den gleichen Griinden lassen sich wertvolle Reinigungsmethoden wie Chromatographie*), Hochvakuum-1) G. BAHR und R. GELIUS, Chem. Ber. 91, 812 [1958], vorstehend. 2) Diese Methode war erfolgreich zur Reinigung yon Tetra-naphthyl-(1)-germanium; vgl. R. WEST, J. Amer. chem. SOC. 74, 4363 [19521.

Recent Developments in Organotin Chemistry

“…32,2161 (1962). salts [30d], sulfur [30e], o r by acids with dissociation constants from 10-1 to 10-10 [31], the stability of the tetraphenyl derivatives 1321, and the formation and stability of tetraalkyltin compounds containing bulky aromatic groups [33] have been studied.…”

Comparisons of organic Group IVB lithium compounds

“…In two cases relatively discrete compounds, eicosaethylcyclodecatin and hexadeca-_n-butylcyclooctatin, appear to have been obtained (81), Treat ment of stannous chloride with a Grignard reagent may lead directly to the hexaorganoditin (59,63). A rather thorough investigation of the products of the interaction of stannous chloride with phenylmagnesium bromide in a 1:6 molar ratio showed the presence of three products: hexaphenylditin, tetraphenyltin, and the supposed tetrakis(triphenylstannyl)tin (54).…”

“…The products obtained under the conditions of the latter workers are bis(triethyltin)oxide and diethyltin oxide, and a free radical chain mechanism is involved. Elemental sulfur has been shown to react with hexamethylditin in benzene to form bis (trimethyltin) sulfide Reaction with alcoholic silver nitrate has been used as a qualita tive test for the ditin linkage, and a variety of compounds,including aryl derivatives, have been shown to deposit a silver mirror on treatment with the reagent (59,62,63,76,123). Potassium permanganate is also reduced readily (63,124).…”

“…Elemental sulfur has been shown to react with hexamethylditin in benzene to form bis (trimethyltin) sulfide Reaction with alcoholic silver nitrate has been used as a qualita tive test for the ditin linkage, and a variety of compounds,including aryl derivatives, have been shown to deposit a silver mirror on treatment with the reagent (59,62,63,76,123). Potassium permanganate is also reduced readily (63,124). Hexaphenylditin has been shown to react virtually quantitatively to produce triphenyltin hydroxide when subjected to the action of potassium permanganate in acetone solution (124) Reaction with chlorine in some cases results in cleavage of organic groups from tin as well as the expected tin-tin scission (123,133).…”