Wir haben zwei neue Nickel-Komplexe dargestellt, das 1 3 -Cyclooctadien-nickel-bromid, CsHlzNiBr, und das 1,5-Cyclooctadien-nickel-jodid, CsH12NiJ. x-Allyl-nickel-halogenid wird in Anwesenheit von Norbornen (geringer ifberschu8) mit 1,5-Cyclooctadien (20-bis 30-facher UberschuD) in n-Heptan bci Zimmertemperatur umgesetzt. Zwei bis drei Stunden nach Beginn der Reaktion schciden sich die Komplexe als gut ausgebildete Kristalle ab. Ausbeute nach 15 Stunden ca. 75 %.Der Komplex CsH12NiJ kann auch direkt durch Erhitzen einer Losung von n-Allyl-NiJ in 1,5-Cyclooctadien auf ca. 80 "C und langsames Abkuhlen gewonnen werden; Ausbcute
Hitherto it has not been possible to synthesize pentalene or its simple derivatives "1. Like fulvene, pentalene should be stabilized by electron donors in the 1-or 3-position [Zl. Synthesis of the thermally stable 1,3-bis(dimethylamino)pentalene (7) has now confirmed this hypothesis.Cyclopentadienylsodium ( I ) in tetrahydrofuran reacts at 20°C with the complex (2) (a yellow, viscous oil) obtained from tetra-N-methylmalonodiamide and triethyloxonium tetrafluoroborate, yielding the fulvene derivative ( 3 ) {yield affords the immonium perchlorate (6) (yield 95 %) as yelfow needles (from CH3CN), decomp. > 150 "C, Amax = 253 mp (log E = 4.47), 260 (4.48), 359 (4.11), 3.97 (4.30) in CH3CN, NMR spectrum (in [Dsldimethyl sulfoxide) 3 singlets at T = 3.04 ( 3 olefinic ring protons), 5.43 (CHz), and 6.50 12 N(CH3)zI.
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