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首页> 外文期刊>New Journal of Chemistry >Probing the factors that influence the conformation of a guanidinato ligand in [(eta(5)-C5Me5)M(NN)X] (NN = chelating N,N ',N ''-tri(o-substituted aryl)guanidinate(1-); X = chloro, azido and triazolato)
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Probing the factors that influence the conformation of a guanidinato ligand in [(eta(5)-C5Me5)M(NN)X] (NN = chelating N,N ',N ''-tri(o-substituted aryl)guanidinate(1-); X = chloro, azido and triazolato)

机译：探测影响胍酰胺配体符合[（η（5）-C5ME5）M（NN）X]（NN = Chelating N，N'，N''-Tri（O-取代的芳基）胍酸（1 - ）; X =氯，Azido和三唑托）

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摘要

Three types of half sandwich complexes, namely, [(eta(5)-Cp*)M(NN)X] (Cp* = C5Me5; NN = chelating N,N',N"-tri(o-substituted aryl)guanidinate(1-) ligand; M = Rh/Ir; X = Cl (9-13), N-3 (14-18) and N3C2(C(O)OR2 (19-21)), were prepared and isolated in moderate to good yields. The new complexes were fully characterized and further molecular structures of key complexes from each type were determined by single crystal X-ray diffraction (SCXRD). The new complexes revealed syn-syn (10, 12, 15 and 20), anti-anti (13 and 16) and anti-syn (14, 17, 19 center dot CHCl3 and 21) conformations. DFT calculations were performed on four conformers of 14, which revealed the stability order as syn-syn (0.00 kcal mol(-1)) anti-syn (0.23 kcal mol(-1)) " syn-anti (3.15 kcal mol(-1)) " anti-anti (5.15 kcal mol(-1)). An intra-ligand repulsive interaction between the o-substituent in two proximal aryl rings in guanidinate ligands of 14 and 17 was invoked as a driving force for the observance of the anti-syn conformer in the solid state, which is likely formed from a hypothetical syn-syn conformer via a guanidine centered rearrangement. The influence of packing forces upon the anti-syn conformation of the guanidinate ligand in 14 was also discussed. NBO analysis was carried out on the N3 moiety of the syn-syn conformer of 14 in order to identify the likely resonance form responsible for [3+2] cycloaddition with the alkyne. Several new complexes that contain an o-substituted arylguanidinate ligand were shown to exist as a mixture of conformers in solution as revealed by NMR spectroscopy, and these conformers were shown to arise from a solid state conformer via guanidinine centered rearrangement.
机译：三种类型的半三明治复合物，即[（eta（5）-cp *）m（nn）x]（cp * = c5me5; nn = chelating n，n'，n“-tri（O-取代的芳基）胍酯（1-）配体; m = rh / Ir; x = Cl（9-13），N-3（14-18）和N3C2（C（O）OR2（19-21））被制备并中等分离良好的收益率。通过单晶X射线衍射（SCXRD）确定新的复合物，从每种类型的关键复合物的进一步分子结构。新复合物揭示了同步型（10,12,15和20），抗抗（13和16）和抗SYN（14,17,19中心点CHCL3和21）构象。DFT计算在14的四个整形剂上进行，其显示稳定性顺序为同步序（0.00kcal摩尔（ -1））＆抗合并（0.23千瓦摩尔（-1））“同步（3.15千瓦摩尔（-1））”抗抗（5.15千瓦摩尔（-1））。一个intra-ligand令人厌恶将O-取代基在14和17的近端芳基环中的相互作用被调用为遵守抗合并的驱动力在固态中的塑造剂，其可能通过假假设的同步组合器通过胍啶中心重排形成。还讨论了填料力对14中的胍酸盐配体抗SYN构象的影响。 NBO分析在14的同步组合器的N3部分上进行，以鉴定负责[3 + 2]环加成的可能的共振形式与炔烃。显示含有O-取代芳基胍丁烷酸盐配体的几种新络合物作为NMR光谱揭示的溶液中的壳体的混合物存在，并且显示这些塑造剂通过胍尼嗪中心重新排列来源于固态化合物。

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