Metallabicyclo[3.1.0]hexene und deren Umlagerung zu Vinylmetallacyclobutenen (M = Ti, Zr)
Metallabicyclo[3.1.0]hexene und deren Umlagerung zu Vinylmetallacyclobutenen (M = Ti, Zr)
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金属双环[3.1.0]己烯和乙烯基金属环丁烯的分解 (M = Ti, Zr)
DOI：
10.1002/cber.19931260707
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发表时间：
1993
期刊：
影响因子：
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通讯作者：
R. Mynott
中科院分区：
文献类型：
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作者：
P. Binger;P. Müller;Franz Langhauser;F. Sandmeyer;Petra Philipps;Barbara Gabor;R. Mynott
金属双环[3.1.0]己烯及其重排为乙烯基金属环丁烯(M=Ti, Zr)
炔烃-茂金属络合物，例如炔二茂钛 1a、b、炔二茂钛 2a、b 和炔二茂锆 5a–d 很容易与 3,3-二甲基环丙烯 (3a) 和 3,3-二苯基环丙烯 (3b) 反应，得到相应的双(η5-环戊二烯基)-金属双环[3.1.0]己烯衍生物4a–e, (M=Ti) 和6a–g (M=Zr) 的产率很高。以类似的方式，Ti或Zr的金属双环[3.1.0]己烯衍生物可以由1，2-二苯基环丙烯(三甲基膦)茂金属9和10以及2-丁炔制备以产生11和12，并由苯炔3a或3b制备以产生8a和8b。当将这些金属双环[3.1.0]己烯衍生物加热至60-80°C数小时后，其中一些金属双环[3.1.0]己烯衍生物会定量重排为相应的4-(二甲基乙烯基)-1-金属-2-环丁烯衍生物16和17a以及4-(二苯基乙烯基)-1-金属-2-环丁烯15c和17a-c。 4-(二苯基乙烯基)-1-钛-2-环丁烯衍生物15a-c也可以通过[(2,2-二苯基乙烯基)卡宾](三甲基膦)-二茂钛(13)与二取代炔烃如甲苯烷、苯基三甲基甲硅烷基乙炔和双(三甲基甲硅烷基)乙炔反应得到。与其他炔烃，例如2-丁炔、1-丁炔、1-丙炔或乙炔，13通过这些炔的聚合反应；在反应混合物中未检测到相应的4-乙烯基-1-环丁烯钛衍生物。所有新的金属环都通过光谱方法进行了充分表征，广泛的 1H 和 13C-NMR 研究为其结构提供了明确的证据。
Metallabicyclo[3.1.0]hexenes and Their Rearrangement to Vinylmetallacyclobutenes (M=Ti, Zr)
Alkyne-metallocene complexes, e.g. the alkynetitanocenes 1a, b, the alkyne(trimethylphosphane)titanocenes 2a, b and the alkyne(trimethylphosphane)zirconocenes 5a–d react readily with 3,3-dimethylcyclopropene (3a) and 3,3-diphenylcyclopropene (3b) to give the corresponding bis(η5-cyclopentadienyl)-metallabicyclo[3.1.0]hexene derivatives 4a–e, (M=Ti) and 6a–g (M=Zr) in high yields. In an analogous manner, metallabicyclo[3.1.0]hexene derivatives of Ti or Zr can be prepared from 1,2-diphenylcyclopropene(trimethylphosphane)metallocenes 9 and 10 and 2-butyne to yield 11 and 12 and from benzyne 3a or 3b to yield 8a and 8b. Some of these metallabicyclo[3.1.0]hexene derivatives rearrange quantitatively to the corresponding 4-(dimethylvinyl)-1-metalla-2-cyclobutene derivates 16 and 17a and 4-(diphenylvinyl)-1-metalla-2-cyclobutenes 15c and 17a–c when they are heated to 60–80°C for several hours. The 4-(diphenylvinyl)-1-titana-2-cyclobutene derivatives 15a–c can also be obtained by reaction of [(2,2-diphenylvinyl)carbene](trimethylphosphane)-titanocen (13) with disubstituted alkynes such as tolane, phenyltrimethylsilylacetylene and bis(trimethylsily)acetylene. With other alkynes, e.g. 2-butyne, 1-butyne, 1-propyne or acetylene, 13 reacts by polymerization of these alkynes; the corresponding 4-vinyl-1-titanacyclobutene derivatives could not be detected in the reaction mixture. All new metallacycles are fully characterized by spectroscopic methods, extensive 1H- and 13C-NMR studies provide unambiguous proof of their structures.