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Methyl Displacements from Cyclopentadienyl Ring Planes in Sterically Crowded (C_5Me_5)_3M Complexes

机译:(C_5Me_5)_3M配合物中的环戊二烯基环平面中的甲基置换

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摘要

The displacements of the methyl substituents away from the metal and out of the cyclopentadienyl ring plane are compared in sterically crowded (C_5Me_5)_3M complexes vs sterically normal f-element complexes in an attempt to evaluate the utility of this parameter in predicting unusual (C_5Me_5)~(1-) ring reactivity.The out-of-plane displacements of 16 sterically crowded tris(cyclopentadienyl) complexes of general formula (C_5Me_5)_3M,(Cs_5Me_4R)_3M (R=Et,'Pr,~tBu,SiMe_3),(C_5Me_5)_3MX (X=anion),and (C_5Me_5)_3ML (L=neutral ligand) are compared with [(C_5Me_5)_2U]_2(C_6H_6),(C_5Me_5)_2Sm(PC_4H_2~tBu_2),and 33 representative examples of f-element bis(cyclopentadienyl) complexes with normal cyclopentadienyl behavior and coordination numbers ranging from 6 to 10.In general,the methyl displacement values of sterically crowded complexes overlap with those in the other complexes,which demonstrates that the basis of the structural distortions is complex.However,if the most extreme out-of-plane displacement in each of the sterically crowded complexes is examined vs the analogous maximum out-of-plane displacement in less crowded systems,there appears to be a basis for predicting cyclopentadienyl reactivity.
机译:比较空间拥挤的(C_5Me_5)_3M配合物与空间正常的f元素配合物中甲基取代基远离金属和环戊二烯基环平面的位移,以尝试评估此参数在预测异常(C_5Me_5)中的效用〜(1-)环反应性。通式(C_5Me_5)_3M,(Cs_5Me_4R)_3M(R = Et,'Pr,〜tBu,SiMe_3)的16种空间拥挤的三(环戊二烯基)配合物的平面外位移,比较[C_5Me_5)_3MX(X =阴离子)和(C_5Me_5)_3ML(L =中性配体)与[(C_5Me_5)_2U] _2(C_6H_6),(C_5Me_5)_2Sm(PC_4H_2〜tBu_2)和33个代表性实例具有正常环戊二烯基行为和配位数为6至10的f元素双(环戊二烯基)配合物。通常,空间拥挤配合物的甲基位移值与其他配合物的甲基位移值重叠,这表明结构扭曲的基础是复杂。但是,如果是最极端的平面外研究了每个空间拥挤复合物中的位移与拥挤程度较低的系统中类似的最大平面外位移,这似乎是预测环戊二烯反应性的基础。

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