PREPARATION, CHARACTERIZATION, AND KINETIC-STUDIES OF GROUP-4 METALLOCENE COMPLEXES WITH TRIPHENYLSILANETELLUROLATE LIGANDS
PREPARATION, CHARACTERIZATION, AND KINETIC-STUDIES OF GROUP-4 METALLOCENE COMPLEXES WITH TRIPHENYLSILANETELLUROLATE LIGANDS
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DOI：
10.1021/om00023a056
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发表时间：
1994-11-01
期刊：
影响因子：
2.8
通讯作者：
ARNOLD, J
中科院分区：
文献类型：
--
作者：
GINDELBERGER, DE;ARNOLD, J
一系列新的化合物纳入三苯基硅烷碲酸盐配体已被制备和表征。通过将碲插入到（THF）（3）LiSiPh（3）的Li-Si键中制备了所需的起始原料，从而以高产率得到（THF）（3）LiTeSiPh（3）。（THF）（3）LiTeSiPh（3）与三氟乙酸的质子分解导致碲醇HTeSiPh（3）的形成，这是第一个被结构表征的碲醇;它在单斜空间群C2/c中结晶，具有a 16.208（3）埃，B = 11.343（3）埃，c = 19.979（3）埃，β = 114.45度，Z = 8，R = 0.0328，R（w）= 0.0409。由（THF）（3）LiTeSiPh（3）与Ph（3）SiCl反应制备了二硅碲化物Te（SiPh（3））（2）。金属茂化合物（RCp）（2）M（TeSiPh（3））（2）（M = Ti，R = H，Me（Cp ′）; M = Zr，R = H，Bu（t）（Cp（t））; M = Hf，R = H，Bu（t））通过用（THF）（3）LiTeSiPh（3）处理适当的金属茂二氯化物来制备。Cp（2）（t）Zr（TeSiPh（3））（2）与叔丁基吡啶的反应得到Te（SiPh（3））（2）的完全消除，形成（Cp（2）（t）ZrTe）（2）作为唯一含金属的产物。动力学研究表明，该反应是一级的茂金属碲酸盐，暗示的机制，涉及分子内消除二甲硅碲。还描述了Cp（2）Zr（TeSiPh（3））（2）的X射线结构;它在单斜空间群P2（1）/n中结晶。其中a = 9.460（1）埃，B = 26.177（2）埃，c 16.442（1）埃，β = 96.79（1）度，Z = 4，R = 0.0277，以及R（w）= 0.0313。
A range of new compounds incorporating the triphenylsilanetellurolate ligand has been prepared and characterized. The required starting material was prepared by insertion of tellurium into the Li-Si bond of(THF)(3)LiSiPh(3), which gave (THF)(3)LiTeSiPh(3) in high yield. Protonolysis of (THF)(3)LiTeSiPh(3) with trifluoroacetic acid resulted in the formation of the tellurol HTeSiPh(3) which is the first tellurol to be structurally characterized; it crystallized in the monaclinic space group C2/c with a 16.208(3) Angstrom, b = 11.343(3) Angstrom, c = 19.979(3) Angstrom, beta = 114.45 degrees, Z = 8, R = 0.0328, and R(w) = 0.0409. The disilyl telluride Te(SiPh(3))(2) was prepared by reaction of (THF)(3)LiTeSiPh(3) with Ph(3)SiCl. The metallocene compounds (RCp)(2)M(TeSiPh(3))(2) (M = Ti, R = H, Me (Cp'); M = Zr, R = H, Bu(t) (Cp(t)); M = Hf, R = H, Bu(t)) were made by treatment of the appropriate metallocene dichloride with (THF)(3)LiTeSiPh(3). Reaction of Cp(2)(t)Zr(TeSiPh(3))(2) with tert-butylpyridine gave clean elimination of Te(SiPh(3))(2) to form (Cp(2)(t)ZrTe)(2) as the only metal-containing product. Kinetic studies showed the reaction to be first-order in metallocene tellurolate, implicating a mechanism involving intramolecular elimination of disilyl telluride. The X-ray structure of Cp(2)Zr(TeSiPh(3))(2) is also described; it crystallized in the monaclinic space group P2(1)/n. with a = 9.460(1) Angstrom, b = 26.177(2) Angstrom, c 16.442(1) Angstrom, beta = 96.79(1)degrees, Z = 4, R = 0.0277, and R(w) = 0.0313.