Nitrogen-Functionalized Cyclopentadienyl Ligands with a Rigid Framework: Complexation Behavior and Properties of Cobalt(I), -(II), and -(III) Half-Sandwich Complexes
Nitrogen-Functionalized Cyclopentadienyl Ligands with a Rigid Framework: Complexation Behavior and Properties of Cobalt(I), -(II), and -(III) Half-Sandwich Complexes
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DOI：
10.1021/om0007163
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发表时间：
2001-02
期刊：
影响因子：
2.8
通讯作者：
M. Enders;A. Ludwig;H. Pritzkow
中科院分区：
文献类型：
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作者：
M. Enders;A. Ludwig;H. Pritzkow
2 - 锂化 - N,N - 二甲基苯胺与2,3,4,5 - 四甲基环戊烯酮反应生成1 - [2 - (N,N - 二甲基氨基苯基) - 2,3,4,5 - 四甲基环戊二烯(2)。如同在1 - (8 - 喹啉基) - 2,3,4,5 - 四甲基环戊二烯(1)中一样，N - 供体通过一个刚性的C₂间隔基与Cp环相连。Co₂(CO)₈分别与1或2反应，生成CoI - 二羰基半夹心配合物7和3。光照会生成具有Co - Co双键的双核配合物4和8。用碘可以氧化3或7a。7a直接形成喹啉与金属配位的CoIII配合物9，而3生成单羰基二碘配合物5。在二氯甲烷中温和加热时，5失去一氧化碳生成钴配合物6，呈现分子内氮配位。二甲基苯胺取代的环戊二烯基化合物10与CoCl₂反应生成CoII配合物11。CoIII配合物6和CoII配合物11用甲基铝氧烷(MAO)处理，得到用于……的低活性催化剂
Reaction of 2-lithio-N,N-dimethylaniline with 2,3,4,5-tetramethylcyclopentenone yields 1-[2-(N,N-dimethylaminophenyl)-2,3,4,5-tetramethylcyclopentadiene (2). As in 1-(8-quinolyl)-2,3,4,5-tetramethylcyclopentadiene (1), the N-donor is connected to the Cp ring by a rigid C2 spacer. Co2(CO)8 reacts with 1 or 2 to give the CoI-dicarbonyl half-sandwich complexes 7 and 3, respectively. Irradiation leads to the binuclear complexes 4 and 8 with a Co−Co double bond. Oxidation of 3 or 7a is possible with iodine. Whereas 7a directly forms the CoIII complex 9 with coordination of the quinoline to the metal, 3 yields the monocarbonyldiiodo complex 5. Upon gentle heating in dichloromethane, 5 loses carbon monoxide to give the cobalt complex 6, displaying intramolecular nitrogen coordination. Reaction of the dimethylaniline-substituted cyclopentadienide 10 with CoCl2 yields the CoII complex 11. The CoIII complex 6 and the CoII complex 11 were treated with methylaluminoxane (MAO) and gave low-activity catalysts for the p...