on cluster, RR′Si(Cl)CCo3(CO)9, is described. The alkoxy derivatives react with i-Bu2AlH or BF3 · Et2O to give the corresponding silicon hydride or fluoride. Reaction of methylidynetricobalt nonacarbonyl with opticallyactive silanes of germane gave the opticallyactive cluster complexes R1R2R3M*CCo3(CO)9 (M* = Si, Ge). These compounds react with phosphine to give the monosubstituted R1R2R3M*CCo3(CO)8(PR3
描述了含有九碳三羰基碳原子团RR'Si(Cl)CCo 3(CO)9的手性氯硅烷的制备和醇解。烷氧基衍生物与i-Bu 2 AlH或BF 3 ·Et 2 O反应,得到相应的氢化硅或氟化硅。亚甲基炔丙基九碳羰基与锗烷的旋光性硅烷反应,得到旋光性簇络合物R 1 R 2 R 3 M * CCo 3(CO)9(M * = Si,Ge)。这些化合物与膦反应生成单取代的R 1 R 2R 3 M * CCo 3(CO)8(PR 3(M * = Si,Ge)。非对映异构体在MePhSi(Obornyl)CCo 3(CO)9配合物的情况下已得到解决。
Use of an optically active germanium species for the resolution of diastereoisomeric transition metal complexes with five different and independent ligands
Reaction of opticallyactive MePh(1-C10H7)GeLi with (η5-C5H5)M(CO)2NO (M = Mo, W) results in replacement of CO and formation of anionic species which can be alkylated with CH3I to afford mixtures of diastereoisomericcomplexes, (η5-C5H5)M(CO)(NO)(GeR3)CH3 (R3 = MePh(1-C10H7); M = Mo, W). These complexes are the first in which a transition metal, surrounded by fivedifferentligands shows optical activity
光学活性的麦菲反应(1-C 10 H ^ 7)用格力(η 5 -C 5 H ^ 5)M(CO)2 NO(M =钼,钨)的结果在更换CO的形成和阴离子物质的其可以是用CH烷基化3我,得到非对映异构物,(η的混合物5 -C 5 H ^ 5)M(CO)(NO)(GER 3)CH 3(R 3 =麦菲(1-C 10 H ^ 7); M = Mo,W)。这些配合物是第一个被五个不同配体包围的过渡金属显示光学活性的化合物。这些化合物不是助熔剂,并且显示出高的光学稳定性。在强迫条件下,分解发生在差向异构之前。
Stereochemistry of a Chiral Germyl Radical in the Reaction of Carbon Tetrachloride
作者:Kunio Mochida、Takato Yamauchi、Hideki Sakurai
DOI:10.1246/bcsj.62.1982
日期:1989.6
and the relative rate of chlorineabstraction to inversion (kCl⁄kinv) of the chiral germyl radical was found to be (0.52±0.13) mol−1 dm3 at 80 °C. The rate constant for the chlorineabstraction (kCl) by germyl radicals with CCl4 was determined to be (6.6±1.0)×108 s−1 mol−1 dm3 by laser-photolysis experiments. By using this rate constant, the kinv value for the chiral germyl radical was estimated to