作者:William Levason、David Pugh、Gillian Reid
DOI:10.1021/ic400077z
日期:2013.5.6
suggested six-coordinate silicon phosphines would be unstable, and also contrasts with the failure to isolate complexes with SiF4 (George et al. Dalton Trans. 2011, 40, 1584–1593). No reaction occurred between phosphines and SiI4, or with SiX4 and arsine ligands including AsMe3 and o-C6H4(AsMe2)2. Attempts to make five-coordinate [SiX4(PR3)] using the sterically bulky phosphines, PtBu3, PiPr3, or PCy3 failed
SiX 4(X = Cl或Br)与PMe 3在无水CH 2 Cl 2中的反应形成反式-[SiX 4(PMe 3)2 ],而二膦,Me 2 P(CH 2)2 PMe 2,Et 2 P(CH 2)2 PET 2,和直径: -C 6 H ^ 4(PME 2)2形式的顺式- [六4(二膦)],全部包含六个坐标的硅中心。与我2 PCH 2 PME 2产物是反式- [的SiCl 4(κ 1 -Me 2 PCH 2 PME 2)2 ]。通过X射线晶体学,显微分析,IR和多核(1 H,13 C 1 H}和31 P 1H})NMR光谱。该配合物是稳定的固体,在非供体溶剂中没有明显的分解,尽管它们对水分和氧气非常敏感。这与最近的密度泛函理论的预测(DFT)计算稳定性冲突(Wilson等。Inorg。化学。2012,51,7657-7668),该建议的六配位硅膦将是不稳定的,并且还与故障对比分离物配合物的SiF