1,4-Dihydro-1,4-diarsinine-Bridged Dinuclear trans-Dihaloplatinum(II) Complexes: Synthesis and Controlled Pt-Pt interaction by Halogen Substitution Induced Conformational Change
1,4-Dihydro-1,4-diarsinine-Bridged Dinuclear trans-Dihaloplatinum(II) Complexes: Synthesis and Controlled Pt-Pt interaction by Halogen Substitution Induced Conformational Change
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1,4-二氢-1,4-二胂桥联双核反式二卤铂(II)配合物：通过卤素取代诱导构象变化合成和控制 Pt-Pt 相互作用
DOI：
10.1021/om100201x
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发表时间：
2010
期刊：
影响因子：
2.8
通讯作者：
Y.; Chujo,Y.:
中科院分区：
文献类型：
--
作者：
Arita;M.; Naka;K.; Shimamoto;T.;Yumura;T.; Nakahashi;A.; Morisaki;Y.; Chujo,Y.:
使用顺式-1,4-二氢-1,4-二甲基-2,3,5,6-四(叔丁氧羰基)-1,4-二胂(cis-DHDAtBu)分别制备单核和双核反式-二氯铂(II)络合物，即反式-PtCl2(cis-DHDAtBu)2和反式,反式-Pt2Cl4(cis-DHDAtBu)2，其中通过五甲基环五胂（环-（MeAs）5）和乙炔二甲酸二叔丁酯的自由基反应制备，通过化学计量添加顺式双（苯甲腈）二氯铂tocis-DHDAtBu单独获得作为唯一产物。将KI加入反式PtCl2(cis-DHDAtBu)2和反式,反式-Pt2Cl4(cis-DHDAtBu)2的丙酮溶液中,用碘化物代替氯化物,分别得到反式-PtI2(cis-DHDAtBu)2和反式,反式-Pt2I4(cis-DHDAtBu)2。所有获得的化合物的结构均通过 1 H 和 13 C NMR 谱、X 射线晶体学和元素分析证实。在一系列现有的铂(II)配合物中，砷周围的内角和As−CC键角显着变化。这些观察结果表明，砷中心周围键角的灵活性是本有机砷化合物的固有特性。使用顺式-DHDAtBu，通过用碘化物取代氯化物，在双核铂(II)“面对面”配合物中诱导金属间相互作用。与反式,反式-Pt2Cl4(cis-DHDAtBu)2相比,反式,反式-Pt2I4(cis-DHDAtBu)2的Pt−Pt距离缩短,并且在反式,反式-Pt2I4(cis-DHDAtBu)2溶液中在562 nm附近观察到新的宽吸收带。密度泛函理论计算表明，前线分子轨道 intrans,trans-Pt2Cl4(cis-DHDAOH)2（其中使用 H 原子替代物代替 tBu 基团）没有显示 dd 相互作用轨道。另一方面，反式的HOMO能级，反式-Pt2I4(cis-DHDAOH)2在π*-反键MO中主要有dxz贡献。
Mono- and dinucleartrans-dichloroplatinum(II) complexes, i.e.,trans-PtCl2(cis-DHDAtBu)2andtrans,trans-Pt2Cl4(cis-DHDAtBu)2, respectively, usingcis-1,4-dihydro-1,4-dimethyl-2,3,5,6-tetrakis(tert-butoxycarbonyl)-1,4-diarsinine (cis-DHDAtBu), which was prepared by the radical reaction of pentamethylcyclopentaarsine (cyclo-(MeAs)5) and di-tert-butyl acetylenedicarboxylate, were obtained individually as only products by stoichiometric addition ofcis-bis(benzonitrile)dichloroplatinum tocis-DHDAtBu. Replacement of chloride with iodide by adding KI into acetone solutions oftrans-PtCl2(cis-DHDAtBu)2andtrans,trans-Pt2Cl4(cis-DHDAtBu)2gavetrans-PtI2(cis-DHDAtBu)2andtrans,trans-Pt2I4(cis-DHDAtBu)2, respectively. The structures of all the obtained compounds were confirmed by1H and13C NMR spectra, X-ray crystallography, and elemental analysis. The interior angles around the arsenic and the As−CC bond angle were significantly varied in a series of the present platinum(II) complexes. These observations suggest that the flexibility of the bond angles around the arsenic center is an inherent property in the present organoarsenic compounds. The intermetallic interaction was induced in the dinuclear platinum(II) “face-to-face” complex usingcis-DHDAtBu by the replacement of chloride with iodide. The distance of the Pt−Pt oftrans,trans-Pt2I4(cis-DHDAtBu)2was shortened compared with that oftrans,trans-Pt2Cl4(cis-DHDAtBu)2, and the new broad absorption band at around 562 nm was observed in the solution oftrans,trans-Pt2I4(cis-DHDAtBu)2. Density functional theory calculations indicate that the frontier molecular orbitals intrans,trans-Pt2Cl4(cis-DHDAOH)2, in which H atom surrogates were used in place of thetBu group, show no d−d interaction orbitals. On the other hand, the HOMO level intrans,trans-Pt2I4(cis-DHDAOH)2has mainly dxzcontributions in the π*-antibonding MO.