Synthesis, Structure, and Properties of 9-Phospha-10-silatriptycenes and their Derivatives
Synthesis, Structure, and Properties of 9-Phospha-10-silatriptycenes and their Derivatives
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DOI：
10.1021/om060681s
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发表时间：
2006-11
期刊：
影响因子：
2.8
通讯作者：
H. Tsuji;Tomoyuki Inoue;Yasuhiro Kaneta;Shohei Sase;and Atsushi Kawachi;K. Tamao
中科院分区：
文献类型：
--
作者：
H. Tsuji;Tomoyuki Inoue;Yasuhiro Kaneta;Shohei Sase;and Atsushi Kawachi;K. Tamao
为了研究9-膦-10-硅三烯(PSiT)的结构和作为膦配体的性质，合成了一系列9-膦-10-硅三烯(PSiT)及其衍生物，如膦硒化合物和顺铂配合物。1J(P−Se)核磁共振偶合常数表明磷原子上孤对轨道具有较大的S特征，这归因于PSiT骨架上较小的C−P−C键角，这一点被X射线晶体学所证实。通过对顺式[PtMe2(PSIT)2]的1J(PT−C)耦合常数的测量，确定了PSIT的强烈反式影响，这是由于两个大的PSIT配体之间的空间排斥导致的络合物中P−铂−P角的增加所致。硅上的取代基和苯环上的桥联都会影响电子性质。硅原子上的吸电子取代基略微增加了磷孤对轨道的S性质，而桥联苯环上的异丙氧基团则略有增加.
A variety of 9-phospha-10-silatriptycenes (PSiT) and some derivatives, such as the phosphine selenides and cis-platinum complexes, have been prepared in order to study their structures and characteristics as a phosphine ligand. The 1J(P−Se) NMR coupling constant of the phosphine selenides demonstrate the large s character of the lone pair orbital on the phosphorus atom, attributable to the small C−P−C bond angles of the PSiT framework, as confirmed by X-ray crystallography. The strong trans influence of PSiT has been determined from the 1J(Pt−C) coupling constant measurements of the cis-[PtMe2(psit)2], which is due to the increase in the P−Pt−P angle in the complexes derived from the steric repulsion between the two bulky PSiT ligands. Both the substituent on the silicon and the bridging benzene rings affect the electronic character. Electron-withdrawing substituents on the silicon atom slightly increase the s character of the phosphorus lone pair orbital, and the isopropoxy groups on the bridging benzene...