Two Types of Intramolecular Lewis-Base Adducts with the [2-(Dimethylamino)ethyl]cyclopentadienyl Ligand: Synthesis and Crystal Structures of {η5:η1-C5H4[(CH2)2NMe2]}Ni−I and {η5-μ-C5H4[(CH2)2NMe2]}(Me3P)Ni−InI2†,‡
Two Types of Intramolecular Lewis-Base Adducts with the [2-(Dimethylamino)ethyl]cyclopentadienyl Ligand: Synthesis and Crystal Structures of {η5:η1-C5H4[(CH2)2NMe2]}Ni−I and {η5-μ-C5H4[(CH2)2NMe2]}(Me3P)Ni−InI2†,‡
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两种类型的[2-(二甲氨基)乙基]环戊二烯基配体分子内路易斯碱加合物：{η5:η1-C5H4[(CH2)2NMe2]}Ni−I和{η5-μ-C5H4[的合成和晶体结构(CH2)2NMe2]}(Me3P)Ni−InI2†,‡
DOI：
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发表时间：
1996
期刊：
影响因子：
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通讯作者：
J. Blümel
中科院分区：
文献类型：
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作者：
R. Fischer;Sylvain Nlate;Holger Hoffmann;E. Herdtweck;J. Blümel
本文报道了镍与[2-（二甲氨基）乙基]吡啶配体（CpN）配合物的合成及其反应性。NiBr 2与CpNLi反应生成新的顺磁性茂镍衍生物（CpN）2Ni（1），其结构经1H和13 C NMR、元素分析和质谱表征。该配合物与Ni（CO）_4进行歧化反应，定量得到二聚镍配合物[CpN（CO）Ni]_2（2）。2与KC 8还原裂解，用Me 3SnCl捕获阴离子中间体，得到锡基镍配合物CpN（CO）Ni− SnMe 3（4）。2与Ga 2Cl 4反应生成镓镍配合物（η5-μ-CpN）（CO）Ni-GaCl 2（7），分子内二甲氨基配位到镓中心。2与碘的氧化裂解和CO的释放导致分子内螯合物（η5：η1-CpN）Ni−I（3）。通过将低价卤化铟InX（X = Br，I）插入到化合物中，以良好的产率获得了化合物（η5-μ-CpN）（PR 3）Ni− InI 2，其中R = C6 H5（5）和CH 3（6）。
The synthesis and reactivity of nickel complexes with the [2-(dimethylamino)ethyl]cyclopentadienyl ligand (CpN) are described. The reaction of NiBr2 with CpNLi leads to the new paramagnetic nickelocene derivative (CpN)2Ni (1), which has been characterized by 1H and 13C NMR, elemental analysis, and mass spectroscopy. Synproportionation of this complex with Ni(CO)4 affords quantitatively the dimeric nickel complex [CpN(CO)Ni]2 (2). Reductive cleavage of 2 with KC8 and trapping of the anionic intermediate with Me3SnCl gives the stannyl−nickel complex CpN(CO)Ni−SnMe3 (4). Reaction of 2 with Ga2Cl4 yields the gallium−nickel complex (η5-μ-CpN)(CO)Ni-GaCl2 (7) with intramolecular coordination of the dimethylamino group to the gallium center. Oxidative cleavage of 2 with iodine and liberation of CO leads to the intramolecular chelate (η5:η1-CpN)Ni−I (3). The compounds (η5-μ-CpN)(PR3)Ni−InI2 with R = C6H5 (5) and CH3 (6) are obtained in good yields by insertion of low-valent indium halides InX (X = Br, I) into the...