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首页> 外文期刊>Chemistry: A European journal >Coordination-driven self-assembly, structures, and dynamic properties of diplatinum hexatriynediyl and butadiynediyl complexes in which the sp carbon chains are shielded by Sp(3) carbon chains: Towards endgroup-endgroup interactions
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Coordination-driven self-assembly, structures, and dynamic properties of diplatinum hexatriynediyl and butadiynediyl complexes in which the sp carbon chains are shielded by Sp(3) carbon chains: Towards endgroup-endgroup interactions

机译：配位驱动的自组装，结构和动力学特性的二碳六三炔和丁二炔配合物，其中sp碳链被Sp（3）碳链屏蔽：走向端基-端基相互作用

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Sequential reactions of trans-(C6F5)(P-tol(3)P),Pt(C C)(3)SiEt3 (PtC6,SiEt3) with nBU(4)N(+) F- (THF/methanol), PtCl, KPF6/tBuOK, and CuCl give trans,trans-[(C6F5){(p-tol(3)P)(2)}Pt(C C)(3)Pt{(Pp-tol(3))(2)}(C6F5)] (PtC6Pt) in 95% yield on multigram scales. Reactions of PtC6Pt and Ar2P(CH2)mPAr(2) afford substitution products trans,trans-[(C6F5){(Ar2P(CH2)mPAr(2))}Pt(C C)(3)Pt- {(Ar2P(CH2)(m) PAr2)}(C6F5)] (PtC6Pt-m/Ar; m/Ar=8/p-tol, 78%; 10/Ph, 82%; 11/Ph, 69%; 12/Ph, 57%; 1.4/p-tol, 57%; 14/p-C6H4-tBu, 71%), in which the diphosphines span the square planar platinum endgroups. An analogous reaction with PEt, gives a tetrakis PEt3 complex Pt'C6Pt' (72%). The crystal structures Of PtC6Pt, Pt'C6Pt', PtC6Pt-10/Ph, PtC6Pt-11/Ph, and PtC6Pt-14/p-tol or solvates thereof are compared. In PtC6Pt, the endgroups can avoid van der Waals contact, and define angles of 0 degrees. In PtC6Pt-14/p-tol, the sp(3) chains twist around the sp chain in a chiral double-helical motif, with an endgroup/endgroup angle of 189 degrees. The sp(3) chains are too short to adopt analogous conformations in the other complexes, but laterally shield the sp chain. NMR spectroscopy shows that the helical enantiomers of PtC6Pt-14/p-tol rapidly interconvert in solution at low temperature. A crystal structure of PtC4Pt shows endgroups that are in van der Waals contact and define an angle of 41 degrees. Reactions with Ar2P-(CH2)(8)PAr2 give PtC4Pt-8/Ar (Ar=Ph, 53%; p-tol, 87%). Low-temperature NMR spectroscopy establish non-helical chiral conformations. Electrochemical oxidations of the diplatinum complexes are analyzed, the reversibilities of which decrease with increasing sp chain length.
机译：反式-（C6F5）（对甲苯酚（3）P），铂（CC）（3）SiEt3（PtC6，SiEt3）与nBU（4）N（+）F-（THF /甲醇），PtCl， KPF6 / tBuOK和CuCl给出反式，反式-[（C6F5）{（对-甲苯（3）P）（2）} Pt（CC）（3）Pt {（对-甲苯（3））（2）} （C6F5）]（PtC6Pt），以克为单位，产率为95％。 PtC6Pt和Ar2P（CH2）mPAr（2）的反应可提供取代产物反式，反式-[（C6F5）{（Ar2P（CH2）mPAr（2））} Pt（CC）（3）Pt- {（Ar2P（CH2） （m）PAr2）}（C6F5）]（PtC6Pt-m / Ar; m / Ar = 8 / p-tol，78％; 10 / Ph，82％; 11 / Ph，69％; 12 / Ph，57％ ; 1.4 /对甲苯，57％; 14 / p-C6H4-tBu，71％），其中二膦跨越方形的平面铂端基。与PEt的类似反应，得到四价PEt3复合物Pt'C6Pt'（72％）。比较了PtC6Pt，Pt'C6Pt'，PtC6Pt-10 / Ph，PtC6Pt-11 / Ph和PtC6Pt-14 / p-tol的晶体结构或它们的溶剂化物。在PtC6Pt中，端基可避免范德华接触，并定义0度角。在PtC6Pt-14 / p-tol中，sp（3）链以手性双螺旋基序围绕sp链扭曲，端基/端基角度为189度。 sp（3）链太短，无法在其他复合物中采用类似的构象，但侧向屏蔽了sp链。 NMR光谱显示，PtC6Pt-14 / p-tol的螺旋对映体在低温下会迅速相互转化。 PtC4Pt的晶体结构显示了与范德华接触并定义41度角的端基。与Ar2P-（CH2）（8）PAr2的反应得到PtC4Pt-8 / Ar（Ar = Ph，53％; p-tol，87％）。低温NMR光谱建立了非螺旋手性构象。分析了二铂配合物的电化学氧化，其可逆性随着sp链长度的增加而降低。

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