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首页> 外文期刊>Dalton transactions: An international journal of inorganic chemistry >A DFT study on the mechanism of a novel, regioselective, intramolecular N-pi rearrangement of cis and trans-eta(1)-N-Cp* Rh-hydroxytamoxifen complexes to their eta(6) derivatives; potential breast cancer pharmaceuticals, and fluorescent probes
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A DFT study on the mechanism of a novel, regioselective, intramolecular N-pi rearrangement of cis and trans-eta(1)-N-Cp* Rh-hydroxytamoxifen complexes to their eta(6) derivatives; potential breast cancer pharmaceuticals, and fluorescent probes

机译：DFT研究的新型，区域选择性，分子内N-pi重排的顺式和反式eta（1）-N-Cp * Rh-羟基他莫昔芬络合物形成eta（6）衍生物的机制;潜在的乳腺癌药物和荧光探针

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The previously reported reactions of cis and trans-hydroxytamoxifen drug derivatives, 1 and 2, with [Cp* Rh(L)(3)](2+) complexes (L = H2O, CH3OH), initially provided the kinetically controled eta(1)-N complexes, 4(OTf, CH3OH) and 5(OTf, CH3OH), which underwent a novel, intramolecular, regioselective N-pi rearrangement to provide the eta(6) complexes, 6 and 7. A dramatic solvent effect was also observed on the rate of this N-pi rearrangement in CH3OH or CH2Cl2. Therefore, a DFT study was conducted that provided further mechanistic and thermodynamic data on this N-pi rearrangement. The preferred structures of both the eta(1)-N and cis eta(6) complexes in the two solvents were determined, and a thorough analysis of their geometries and electronic structures has been provided. The influence of the solvent on the N-pi rearrangement was studied by including the solvent both implicitly using a PCM model, and explicitly by introducing the counterion and/or the solvent molecules into the inner and outer coordination spheres of the complexes. It was shown that the triflate (OTf-) counterion was strongly bound in the inner coordination sphere of the eta(1)-N complexes, 4(OTf) and 5(OTf), and in the outer sphere of the coordinatively saturated eta(6) complexes, 6 and 7, especially in non-polar media. The cleavage of the ionic Cp* Rh-OTf bond was found to be the rate-limiting step in the N-pi rearrangement. The thermodynamic results suggested that the eta(6) complexes were more stable than the eta(1)-N complexes in CH2Cl2 and in CH3OH at elevated temperatures. The opposite relationship for the stabilities of the eta(1)-N complexes was found in CH3OH at room temperature, thus corroborating the experimental results that the N-pi rearrangement did not occur, under these conditions. A plausible mechanistic pathway for the N-pi rearrangement was proposed from our extensive DFT studies, that included several important intermediates and transition states, and provided a unique view of this novel transformation.
机译：先前报道的顺式和反式羟基他莫昔芬药物衍生物1和2与[Cp * Rh（L）（3）]（2+）配合物（L = H2O，CH3OH）的反应，最初提供了动力学控制的eta（1） ）-N配合物4（OTf，CH3OH）和5（OTf，CH3OH），它们经历了新型的分子内区域选择性N-pi重排，从而提供了eta（6）配合物6和7。在CH3OH或CH2Cl2中观察到此N-pi重排的速率。因此，进行了DFT研究，提供了有关此N-pi重排的更多机理和热力学数据。确定了两种溶剂中eta（1）-N和顺式eta（6）配合物的优选结构，并对它们的几何形状和电子结构进行了全面分析。通过使用PCM模型隐式包括溶剂，以及通过将抗衡离子和/或溶剂分子引入配合物的内部和外部配位域中来明确地包括溶剂，研究了溶剂对N-pi重排的影响。结果表明，三氟甲磺酸盐（OTf-）抗衡离子牢固地结合在eta（1）-N配合物4（OTf）和5（OTf）的内部配位域以及配位饱和eta（ 6）配合物6和7，特别是在非极性介质中。发现离子Cp * Rh-OTf键的断裂是N-pi重排中的限速步骤。热力学结果表明，在高温下，CH2Cl2和CH3OH中的eta（6）配合物比eta（1）-N配合物更稳定。在室温下，在CH3OH中发现了eta（1）-N配合物的稳定性的相反关系，因此证实了在这些条件下未发生N-pi重排的实验结果。我们广泛的DFT研究提出了一种N-pi重排的合理机制，其中包括几个重要的中间体和过渡态，并为这种新颖的转化提供了独特的见解。

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