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首页> 外文期刊>Chemistry: A European journal >A Molecular Paddlewheel with a Sliding Organometallic Latch: Syntheses, X-Ray Crystal Structures and Dynamic Behaviour of [Cr(CO)(3){eta(6)-2-(9-triptycyl)indene}], and of [M(CO)(3){eta(5)-2-(9-triptycyl)indenyl}] (M=Mn, Re)
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A Molecular Paddlewheel with a Sliding Organometallic Latch: Syntheses, X-Ray Crystal Structures and Dynamic Behaviour of [Cr(CO)(3){eta(6)-2-(9-triptycyl)indene}], and of [M(CO)(3){eta(5)-2-(9-triptycyl)indenyl}] (M=Mn, Re)

机译：具有滑动有机金属闩锁的分子桨轮：[Cr（CO）（3）{eta（6）-2-（9-triptycyl）indene}]和[M（ CO）（3）{eta（5）-2-（9-三苯甲基）茚基}]（M = Mn，Re）

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In [eta(6)-2-(9-triptycyl)-indene]-tricarbonylchromium (2a), the indenyl-chromium moiety is linked directly to the axis of the three-bladed triptycene paddlewheel. However, the molecular structure of 2a reveals that there is no steric interaction between these components, and the paddlewheel is free to rotate. Accordingly, its NMR spectrum indicates the full equivalence of the blades of the triptycene. Deprotonation of the indene induces a haptotropic shift of the organometallic fragment from the six-membered to the five-membered ring of the indene and, in the sodium [eta(5)-2-(9-triptycyl)indenyl]tricarbonylchromium salt (3a), so formed, rotation of the three-bladed molecular paddlewheel is now blocked by the bulky tripod. NMR data for 3a, and also for the isostructural eta(5)-Mn(CO)(3) and eta(5)-Re(CO)(3) complexes, 3b and 3c, respectively, reveal a 2:1 splitting of the blades of the triptycyl moiety, thus breaking its original three-fold symmetry. ne X-ray crystal structures of the chromium complex, 2a, and of the manganese and rhenium complexes, 3b and 3c, provide pictures of the system in both its "ON" and "OFF" states, whereby the M(CO)(3) tripod has moved about 2 angstrom towards the triptycene, thus blocking its rotation. Comparison of the rotational barriers in 2-(9-triptycyl)indene (1) and its complexes 2 and 3, suggests that rotation of the paddlewheel can be slowed by a factor of approximately 10(8).
机译：在[η（6）-2-（9-三烯丙基）-茚]-三羰基铬（2a）中，茚基-铬部分直接连接到三叶三烯桨轮的轴上。但是，2a的分子结构表明这些成分之间没有空间相互作用，并且叶轮可以自由旋转。因此，其NMR光谱表明三并茂叶片完全等效。茚的去质子化诱导有机金属片段从茚的六元环到五元环以及[η（5）-2-（9-三苯甲基）茚基]三羰基铬钠盐（3a ）这样构成的三叶式分子桨轮现在被笨重的三脚架阻止了旋转。 3a的NMR数据以及同构的eta（5）-Mn（CO）（3）和eta（5）-Re（CO）（3）配合物3b和3c的NMR数据分别显示2：1的拆分三蝶烯部分的叶片，从而破坏了其最初的三重对称性。铬配合物2a以及锰和rh配合物3b和3c的X射线晶体结构提供了处于“开”和“关”状态的系统图片，其中M（CO）（3 ）三脚架已向三萜移动约2埃，从而阻止了其旋转。比较2-（9-三苯甲基）茚（1）及其配合物2和3中的旋转势垒，表明桨轮的旋转速度可降低约10（8）。

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