sp Carbon chains surrounded by sp3 carbon double helices: wire-like Pt(CC)nPt moieties that are spanned by two α,ω-diphosphines that bear heteroatoms or alkyl substituents
sp Carbon chains surrounded by sp3 carbon double helices: wire-like Pt(CC)nPt moieties that are spanned by two α,ω-diphosphines that bear heteroatoms or alkyl substituents
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sp 碳链被 sp3 碳双螺旋包围：线状 Pt(CîC)nPt 部分，由两个带有杂原子或烷基取代基的 α,β-二膦跨越
DOI：
10.1039/b708690n
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发表时间：
2007
影响因子：
3.3
通讯作者：
Gladysz, John A.
中科院分区：
文献类型：
--
作者：
de Quadras, Laura;Bauer, Eike B.;Stahl, Jürgen;Zhuravlev, Fedor;Hampel, Frank;Gladysz, John A.
Pt（Ph 2 P（CH 2）2C（CH 3）2（CH 2）8 C（CH 3）2（CH 2）2 PPh 2）（C6 F5）（9），分别与反式跨二膦。反式，反式-（C6 F5）（p-tol 3 P）2 Pt（CRC）4Pt（Pp-tol 3）2（C6 F5）与Ph 2 P（CH 2）2C（CH 3）2（CH 2）8 C（CH 3）2（CH 2）2 PPh 2和p-tol 2 P（CH 2）3（CF2）8（CH 2）3 Pp-tol 2反应得到10（70%），9的异构体具有跨末端的二膦，和氟化二膦的类似加合物。然而，后者在尝试后处理时发生低聚。5的晶体结构表明，sp3链采用手性双螺旋构象的sp链，与端基定义一个164.11角。详细分析了前述复合物的其他构象性质，并通过低温NMR实验探测了动力学性质。
Pt (Ph2P (CH2) 2C (CH3) 2 (CH2) 8C (CH3) 2 (CH2) 2PPh2)(C6F5)(9), with trans-spanning diphosphines, respectively. Reactions of trans, trans-(C6F5)(p-tol3P) 2Pt (CRC) 4Pt (Pp-tol3) 2 (C6F5) with Ph2P (CH2) 2C (CH3) 2 (CH2) 8C (CH3) 2 (CH2) 2PPh2 and p-tol2P (CH2) 3 (CF2) 8 (CH2) 3Pp-tol2 give 10 (70%), the isomer of 9 with termini-spanning diphosphines, and the analogous adduct of the fluorinated diphosphine. However, the latter oligomerizes upon attempted workup. The crystal structure of 5 shows that the sp3 chains adopt a chiral double-helical conformation about the sp chain, with the endgroups defining a 164.11 angle. Additional conformational properties of the preceding complexes are analyzed in detail, and dynamic properties are probed by low temperature NMR experiments.