SYNTHESIS AND CRYSTAL-STRUCTURE OF FISCHER,E.O. RED CRYSTALLINE MODIFICATION OF TRIS-CYCLOPENTADIENYLBISMUTH, ((1)H-C5H(5))(3)BI
SYNTHESIS AND CRYSTAL-STRUCTURE OF FISCHER,E.O. RED CRYSTALLINE MODIFICATION OF TRIS-CYCLOPENTADIENYLBISMUTH, ((1)H-C5H(5))(3)BI
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DOI：
10.1016/0022-328x(94)05012-z
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发表时间：
1995-01-11
影响因子：
2.3
通讯作者：
LI, XW
中科院分区：
文献类型：
--
作者：
LORBERTH, J;MASSA, W;LI, XW
通过三(二烷氨基)铋化合物与单体环戊二烯在四氢呋喃中的酸碱反应，制得了三环戊二烯基铋的E.O.Fischer红晶型修饰产物BiC5H5(3)。从乙醚中结晶得到了透明的深红色晶体，产率为70%；作为该反应的副产物，还分离出了一种聚合物，单价铋化合物，环戊二烯基铋(I)，(BiC5H5)(无穷大)。用单晶X射线衍射法测定了‘’红色铋(C5H5)(3)‘’的晶体结构：单斜晶系，空间群P2(1)/c，a=8.898(4)b=8.684(3)，c=17.945(7)埃，β=17.945(4)度，Z=4。这种变色现象可能是由于一个分子中的铋原子与相邻分子中的一个环戊二烯配体相互作用的结果。
E.O. Fischer's red crystalline modification of tris-cyclopentadienylbismuth, Bi(C5H5)(3), was obtained by acid-base reaction of tris(dialkylamino)bismuth compounds with monomeric cyclopentadiene in THF. Crystallisation from ether gave transparent deep red crystals in 70% yield; as a by-product of this reaction, a polymeric, monovalent bismuth compound, cyclopentadienylbismuth (I), (BiC5H5)(infinity) was also isolated. The crystal structure of ''red Bi(C5H5)(3)'' has been determined at - 70 degrees C by single crystal X-ray diffraction methods: monoclinic crystals, space group P2(1)/c, a = 8.898(4) b = 8.684(3), c = 17.945(7) Angstrom, beta = 110.10(4)degrees and Z = 4. On exposure to light a colour change is observed from transparent red to opaque red which is maintained at 15 degrees C. Warming to 20 degrees C the material rapidly turns black. This colour change phenomenon is probably a result of the interaction of the bismuth atom of one molecule with one cyclopentadienyl ligand of a neighbouring molecule of Bi(C5H5)(3).