Balakrishna M S, Panda R, Mague J T
Department of Chemistry, Indian Institute of Technology, Bombay, Powai, Mumbai 400 076, India.
Inorg Chem. 2001 Oct 22;40(22):5620-5. doi: 10.1021/ic010518j.
Bis(dichlorophosphino)aniline, PhN(PCl(2))(2), reacts with stoichiometric amounts of 2,2'-thiobis(4,6-di-tert-butylphenol) to afford a 10-membered heterocycle, PhN(PCl)(2)[(-OC(6)H(2)((t)Bu)(2))(mu-S)(((t))Bu)(2)C(6)H(2)O-)] (1), in high yield. The structure of the heterocycle has been determined by a single-crystal X-ray analysis. The 10-membered heterocycle 1 reacts with SbF(3) to afford the corresponding fluoro derivative 2 in good yield. The compounds 1 and 2 act as tridentate ligands with molybdenum carbonyl derivatives, forming complexes of the type [Mo(CO)(3)[eta(3)-PhN(PX)(2)[(-OC(6)H(2)((t)Bu)(2))(mu-S)(((t)Bu)(2)C(6)H(2)O-)]-kappa P,kappa P,kappa S]] (3 X = Cl, 4 X = F). A crystal structure of the fluoro derivative 4 showed the facial tricarbonyl complex comprising a relatively strain-free tetracyclic structure with molybdenum in an octahedral environment; the two phosphorus and the sulfur centers were the donor atoms. Compound 2 readily reacts with Ru(II), Pd(II), and Pt(II) derivatives to form chelate complexes, demonstrating the eta(2) mode of coordination.
双（二氯膦基）苯胺，即PhN(PCl₂)₂，与化学计量的2,2'-硫代双（4,6-二叔丁基苯酚）反应，高产率地生成一个10元杂环，即PhN(PCl)[(-OC₆H₂((t)Bu)₂)(μ-S)((t)Bu)₂C₆H₂O-] (1)。该杂环的结构已通过单晶X射线分析确定。10元杂环1与SbF₃反应，高产率地生成相应的氟代衍生物2。化合物1和2作为三齿配体与钼羰基衍生物反应，形成[Mo(CO)₃[η³-PhN(PX)₂[(-OC₆H₂((t)Bu)₂)(μ-S)((t)Bu)₂C₆H₂O-]-κP,κP,κS]]类型的配合物（3 X = Cl，4 X = F）。氟代衍生物4的晶体结构表明，面式三羰基配合物具有相对无应变的四环结构，钼处于八面体环境中；两个磷原子和硫原子中心为供体原子。化合物2很容易与Ru(II)、Pd(II)和Pt(II)衍生物反应形成螯合配合物，显示出η²配位模式。
