Über metallorganische Derivate des Acetylens. I

Abstract

Es wird über eine neue Gruppe von Acetylenverbindungen berichtet, in denen die Wasserstoffatome des Acetylens durch metallorganische Reste ersetzt sind. Die Darstellungsmethoden, physikalischen und chemischen Eigenschaften der folgenden Verbindungen werden beschrieben: Unter bestimmten Versuchsbedingungen können Komplexe nachgewiesen werden, die durch Anlagerung eines | C=C‐H−‐Anions an metallorganische Acetylen‐Monosubstitutionsprodukte entstehen.

Organometallic Acetylenes of the Main Groups III-V

“…Silicon and germanium halides, in general, undergo a fast ammonolysis and thus are not capable of forming acetylenic derivatives in this medium. The only products obtained from the reaction of sodium acetylide and organotin and organolead halides were disubstituted acetylenes of the type R3MC=CMR3 (8). Based on this result and a number of experimental observations, a metalation reaction as explanation was excluded and the formation of an intermediate complex, Na[R3M-(C=CH)2], was suggested which in turn decomposes upon removal of the ammonia at room temperature (8).…”

“…The only products obtained from the reaction of sodium acetylide and organotin and organolead halides were disubstituted acetylenes of the type R3MC=CMR3 (8). Based on this result and a number of experimental observations, a metalation reaction as explanation was excluded and the formation of an intermediate complex, Na[R3M-(C=CH)2], was suggested which in turn decomposes upon removal of the ammonia at room temperature (8). Two more recent papers report the successful preparation of triphenylethynyltin and triphenylethynyllead as a result of the rapid addition of the corresponding metal organic iodides to a liquid ammonia-sodium acetylide solution.…”

“…Although the organometallic alkali metal compounds of group IV are well known and relatively easy to prepare, the synthesis of trialkyl (aryl) alkynyl derivatives from the corresponding organometallic alkyl compounds and haloacetylenes has been used for only a relatively small number of tin and lead compounds (8,102,134,249,251,252, 254,255).…”

“…1.4642 96.5-98.5 (8) 1.4641 101-102( 16) 1.4525 122 (5) 1.4725 99.5 (6) 1.4580 Report of synthesis of parent compound could not be found in the 2. Reactions of Alkynylorganosilanes, R^nSi(C=CR)n…”

Poly(dialkylstannane) and poly(diarylstannane) homo- and random copolymers synthesized in liquid ammonia

“…For reference purposes the corresponding homopolymers have also been included (Scheme 2). Conveniently, reactions of this type have found attention in the literature for some time [16][17][18][19] with a focus to form tin-carbon bonds as well as tin-tin bonds, [20][21][22][23][24][25][26][27][28][29][30][31][32][33][34][35] and have been investigated in more detail more recently. 36,37 Notably, delocalization of s-electrons in the backbone of polystannanes was found to be responsible for the characteristic yellow color and the absorption maxima around 390 nm for poly(dialkylstannane)s (s-delocalization).…”