Levason William, Manning Joanna M, Reid Gillian, Tuggey Matthew, Webster Michael
School of Chemistry, University of Southampton, Southampton, UKSO17 1BJ.
Dalton Trans. 2009 Jun 21(23):4569-77. doi: 10.1039/b900321e. Epub 2009 Apr 17.
Simultaneous dropwise addition of thf/EtOH solutions of Se{(CH(2))(3)OTs}(2) and o-C(6)H(4)(CH(2)SeCN)(2) or NCSe(CH(2))(3)SeCN to a suspension of NaBH(4) in thf/EtOH at room temperature yields gram quantities of the 13- and 12-membered triselenoether macrocycles (1) and (2) respectively in high yield. The 11-membered ring (3) is obtained similarly by simultaneous dropwise addition of thf/EtOH solutions of Na(2)[o-C(6)H(4)Se(2)] (itself prepared by NaBH(4) reduction of the polymeric o-C(6)H(4)Se(2)) and Se{(CH(2))(3)OTs}(2) to a suspension of NaBH(4) in thf/EtOH. The small-ring, potentially tridentate Se(2)N(pyridyl)-donor macrocycles (4) and (5) were obtained in essentially quantitative yield by simultaneous dropwise addition of thf/EtOH solutions of 2,6-bis(bromomethyl)pyridine and either o-C(6)H(4)(CH(2)SeCN)(2) or NCSe(CH(2))(3)SeCN to a suspension of NaBH(4) in thf/EtOH at room temperature. (1)-(5) have been characterised by (1)H, (13)C{(1)H} and (77)Se{(1)H} NMR spectroscopy, EI MS, and for (1) and (4), by X-ray crystal structures. Reaction of PtMe(3)I with one mol. equiv. of L (L = (1)-(5)) in refluxing CHCl(3) gives the ionic complexes [PtMe(3)(L)]I cleanly and in good yield. These were characterised by (1)H, (13)C{(1)H}, (77)Se{(1)H} and (195)Pt NMR spectroscopy, electrospray MS, microanalyses and by crystal structures of [PtMe(3)((1))]I and [PtMe(3)((4))]I, which confirm distorted octahedral coordination at Pt(IV), with fac-tridentate coordination of the macrocycle in all cases, with anionic iodide. The complexes [PtCl(2)(L)] (L = (1)-(3)) were obtained as poorly soluble yellow-orange solids by reaction of PtCl(2) with L in MeCN solution. The d(3) Cr(III) complexes of L (L = (1)-(5)) were obtained by reaction with [CrCl(3)(thf)(3)] in anhydrous CH(2)Cl(2) as distorted octahedral fac-[CrCl(3)(L)], as poorly soluble blue-purple through to green powdered solids, which have been characterised by microanalysis, UV-visible and IR spectroscopy and by their magnetic moments. The properties of these complexes are compared with related chalcogenoether complexes from the literature involving thioether and acyclic selenoether coordination.
在室温下，将Se{(CH₂)₃OTs}₂与o-C₆H₄(CH₂SeCN)₂或NCSe(CH₂)₃SeCN的四氢呋喃/乙醇溶液同时逐滴加入到硼氢化钠在四氢呋喃/乙醇中的悬浮液中，可高产率地得到克级量的13元和12元三硒醚大环化合物(1)和(2)。通过将Na₂[o-C₆H₄Se₂]（其由硼氢化钠还原聚合物[o-C₆H₄Se₂]ₙ制备）与Se{(CH₂)₃OTs}₂的四氢呋喃/乙醇溶液同时逐滴加入到硼氢化钠在四氢呋喃/乙醇中的悬浮液中，以类似方式得到11元环(3)。通过将2,6-双(溴甲基)吡啶与o-C₆H₄(CH₂SeCN)₂或NCSe(CH₂)₃SeCN的四氢呋喃/乙醇溶液同时逐滴加入到室温下硼氢化钠在四氢呋喃/乙醇中的悬浮液中，以基本上定量的产率得到小环、潜在三齿的Se₂N(吡啶基)供体大环化合物(4)和(5)。(1)-(5)已通过¹H、¹³C{¹H}和⁷⁷Se{¹H}核磁共振光谱、电子轰击质谱进行了表征，对于(1)和(4)，还通过X射线晶体结构进行了表征。在回流的氯仿中，PtMe₃I与1摩尔当量的L（L = (1)-(5)）反应，可干净地得到离子配合物[PtMe₃(L)]I，产率良好。这些配合物已通过¹H、¹³C{¹H}、⁷⁷Se{¹H}和¹⁹⁵Pt核磁共振光谱、电喷雾质谱、微量分析以及[PtMe₃((1))]I和[PtMe₃((4))]I的晶体结构进行了表征，这些表征证实了Pt(IV)处的扭曲八面体配位，在所有情况下大环均以面式三齿配位，带有阴离子碘化物。通过PtCl₂与L在乙腈溶液中反应，得到溶解性很差的橙黄色固体配合物[PtCl₂(L)]（L = (1)-(3)）。L（L = (1)-(5)）的d³Cr(III)配合物通过与[CrCl₃(thf)₃]在无水二氯甲烷中反应得到扭曲八面体面式-[CrCl₃(L)]，为溶解性很差的蓝紫色至绿色粉末状固体，已通过微量分析、紫外可见光谱和红外光谱以及它们的磁矩进行了表征。将这些配合物的性质与文献中涉及硫醚和无环硒醚配位的相关硫属醚配合物进行了比较。
