SYNTHESIS OF MONOMERIC PERMETHYLYTTROCENE DERIVATIVES - THE CRYSTAL-STRUCTURES OF ETA-5-C5H5YN(SIME3)2 AND ETA-5-C5H5YCH(SIME3)2
SYNTHESIS OF MONOMERIC PERMETHYLYTTROCENE DERIVATIVES - THE CRYSTAL-STRUCTURES OF ETA-5-C5H5YN(SIME3)2 AND ETA-5-C5H5YCH(SIME3)2
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DOI：
10.1021/om00139a034
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发表时间：
1986-08-01
期刊：
影响因子：
2.8
通讯作者：
HUIS, R
中科院分区：
文献类型：
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作者：
DENHAAN, KH;DEBOER, JL;HUIS, R
Cp* 2 YCl-THF（2）与NaN（SiMe 3）2和巫妖（SiMe 3）2反应，分别产生单体配合物Cp* 2 YN（SiMe 3）2（3）和Cp* 2 YCH（SiMe 3）2（4）。用X射线衍射法测定了化合物3和4的晶体结构。化合物3为单斜晶系，空间群P2\jc，a= 11.466（2）A，B= 15.684（8）A，c= 31.557（9）A，B = 96.36（2），Z= 8.将结构精修至R= 0.044。该配合物的分子结构具有显著短的YN距离（2.274（5）和2.253（5）<$）和Y-甲基接触。4的晶体为单斜晶系，空间群J2/c，a= 17.998（8）×，B= 21.758（8）×，c= 14.591（4）×，ß= 92.39（3），Z= 8。将结构精修至R= 0.073。该分子结构除了表现出短的Y-甲基接触外，还表现出“Ce-agostic Y-CH相互作用”。钇-甲基相互作用也通过固态CP 13 C NMR进行了研究。在室温下，3显示了两个和4显示了三个独立的共振的甲基基团键合到硅，支持的结论是，在4中的甲基钇相互作用是强于3。本文报道了Cp* Na（1）的简便合成方法。
The reactions of Cp* 2YCl-THF (2) with NaN (SiMe3) 2 and LiCH (SiMe3) 2 yield the monomeric complexes Cp* 2YN (SiMe3) 2 (3) and Cp* 2YCH (SiMe3) 2 (4), respectively. The crystal structures of 3 and 4 were determined bv X-ray diffraction methods. The crystals of 3 are monoclinic, space group P2\jc, with a= 11.466 (2) A, b= 15.684 (8) Á, c= 31.557 (9) Á, ß= 96.36 (2), and Z= 8. The structure was refined to R= 0.044. The molecular structures of this complex feature remarkably short YN distances (2.274 (5) and 2.253 (5) Á) and Y-methyl contacts. Crystals of 4 are monoclinic, space group J2/c, with a= 17.998 (8) Á, b= 21.758 (8) Á, c= 14.591 (4) Á, ß= 92.39 (3), and Z= 8. The structure was refined to R= 0.073. The molecular structure exhibits besides a short Y-methyl contact an “ce-agostic Y—CH interaction”. The yttrium-methyl interactions were also studied by solid-state CP 13C NMR. At room temperature 3 shows two and 4 shows three separate resonances of methyl groups bonded to silicon, supporting the conclusion that in 4 the methyl-yttrium interaction is stronger than in 3. A convenient synthesis of Cp* Na (1) is described.