Photochemische Reaktionen von Übergangsmetall-Olefin-Komplexen, VII [1] Die Reaktion von Triearbonyl-η6-cyclooctatetraen-chrom(0) mit 6-mono-und 6.6-disubstituierten Fulvenen / Photochemical Reactions of Transition Metal Olefin Complexes, VII [1] The Reactions of Tricarbonyl-η6-cyclooctatetraene-chr

Photochemische Reaktionen von Übergangsmetall-Olefin-Komplexen, VII [1] Die Reaktion von Triearbonyl-η6-cyclooctatetraen-chrom(0) mit 6-mono-und 6.6-disubstituierten Fulvenen / Photochemical Reactions of Transition Metal Olefin Complexes, VII [1] The Reactions of Tricarbonyl-η6-cyclooctatetraene-chr
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过渡金属烯烃配合物的光化学反应,VII [1] 三羰基-η6-环辛四烯-chr 的反应

DOI:
10.1515/znb-1983-0710
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发表时间:
1983
期刊:
Zeitschrift für Naturforschung B
影响因子:
--
通讯作者:
H. Kurz
H. Kurz
中科院分区:
--
文献类型:
--
作者:
C. G. Kreiter;H. Kurz

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三羰基-η6-环辛四烯-铬(0)(1)与6-单取代和6,6-二取代富烯(2-7)发生光化学反应,生成二羰基-η-1′-3“:1”-5“-(环辛-2 ′,4 ′,6 ′-三烯-1 ′,8 ′-亚环戊二烯基-亚环戊二烯基-甲烷)铬络合物(8−13)。三羰基-η-6,6-二甲基富烯-铬(0)(16)与环辛四烯、双环[6,1,0]壬-2,4,6-三烯和反式-9-甲氧基双环-[6,1,0]壬-2,4,6-三烯以类似的方式反应,形成8和2-双环[6,1,0]壬-4 ′,6 ′-二烯-2 ′,3 ′-亚环戊二烯基-2-亚环戊二烯基-丙烷络合物(19,20)。除13外,6-二甲氨基富烯(7)还与1-二羰基-η-1 Mobi,6 ′,7 ′:1″-5″-(2-环庚-2 ′,4 ′,6 ′-三烯-7 ′-亚基-1-环庚烯亚基-1-二甲氨基乙烷)-铬(14)反应,这涉及八元环的意外收缩。通过IR和NMR光谱确定了8 - 15和19 - 20的结构。在Cr(CO)_2 [C(C_6H_5)_2(C_5H_4)(C_8H_8)](9)中,一个苯基表现出绕其两个折叠轴的受阻转动。
Tricarbonyl-η6-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. In Cr(CO)2[C(C6H5)2(C5H4)(C8H8)] (9) one of the phenyl groups shows hindered rotation around its two fold axis.