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Tricarbonyl-η 6 -cyclooctatetraene-chromium(0) (1) reacts photochemically with 6-mono- and 6,6-disubstituted fulvenes (2-7) in a substitution-oxidative rearrangement-reaction to dicarbonyl-η-1′-3':1″-5″-(cycloocta-2′,4′,6′-trien-1′,8′-ylene-cyclopentadienylidene-methane)chromium complexes (8−13). Tricarbonyl-η-6,6-dimethylfulvene-chromium(0) (16) reacts with cyclooctatetraene, bicyclo[6,1,0]nona-2,4,6-triene and anti-9-methoxybicyclo-[6,1,0]nona-2,4,6-triene in a similar manner and forms 8 and 2-bicyclo[6,1,0]nona-4′,6′-dien-2′,3′-ylene-2-cyclopentadienylidene-propane complexes (19, 20). In addition to 13 6-dimethylaminofulvene (7) yields with 1 dicarbonyl-η-1′,6′,7′: 1 ″ -5 ″ -(2-cyclohepta-2′,4′,6′-trien-7′-ylidene-1 -cyclopentadienylidene-1-dimethylamino-ethane)-chromium (14) which involves an unexpected contraction of the eight-membered ring. The constitutions of 8−15 and 19−20 were determined by IR and NMR spectroscopy.

zeitschrift für naturforschung b

Photochemische Reaktionen von Übergangsmetall-Olefin-Komplexen, VII [1] Die Reaktion von Triearbonyl-η 6 -cyclooctatetraen-chrom(0) mit 6-mono-und 6.6-disubstituierten Fulvenen / Photochemical Reactions of Transition Metal Olefin Complexes, VII [1] The Reactions of Tricarbonyl-η 6 -cyclooctatetraene-chromium(0) with 6-Mono-and 6,6-Disubstituted Fulvenes