This paper addresses the problem of the observation of the so-called C-C agostic interactions in cyclopropyl complexes of scandium.Three new cyclopropyl complexes of scandium based on theβ-diketiminato ligand were sy...This paper addresses the problem of the observation of the so-called C-C agostic interactions in cyclopropyl complexes of scandium.Three new cyclopropyl complexes of scandium based on theβ-diketiminato ligand were synthesized including by an intramolecular C-H bond activation reaction in one case.X-ray diffraction analysis revealed distorted cyclopropyl groups in the complexes,and the distortion could be observed in solution as well for one of the complexes thanks to the natural abundance INADEQUATE NMR spectroscopy which showed a markedly reduced J_(C-C)coupling constant.This signature of the C-C agostic interaction was further examined using DFT modelling which,together with NBO calculations,indicated that C-H and C-C agostic interactions are not exclusive but can complement each other,accounting for the distortions.The intramolecular C-H bond activation in the scandium biscyclopropyl complex was investigated by isotopic labeling experiments,which indicated a direct proton abstraction of the isopropyl group in theβ-diketiminato ligand by a cyclopropyl group.展开更多
By employing functional ligand 3,6-bis（3,5-dimethyl-lH-pyrazol-4-yl）-9-methyl- 9H-carbazole, a novel luminescent Ni complex has been obtained. Its structure was characterized by single-crystal X-ray diffraction anal...By employing functional ligand 3,6-bis（3,5-dimethyl-lH-pyrazol-4-yl）-9-methyl- 9H-carbazole, a novel luminescent Ni complex has been obtained. Its structure was characterized by single-crystal X-ray diffraction analysis. Crystal data： monoclinic, space group P2/c, a = 13.4224（18）, b = 13.759（2）, c = 8.0633（17）/~, fl = 96.448（3）~, C23H23NsNi（NO3）2, M,. = 552.19, V = 1479.7（4） A3, Z = 2, Dc = 1.239 g/cm3,/ffMoKa） = 0.700 mm-1, F（000） = 572, the final R = 0.0566 and wR = 0.1336 for 1638 observed reflections with I 〉 2a（/）. X-ray analysis indicates that each metal center coordinates with two N and two H atoms in tetrahedral interaction geometry. Weak interaction between Ni and N atom of pyrazole ligand and agostic bond （Ni...H-N interaction） play important roles in the formation of the 2-dimension framework. Significantly, this framework could pack into a tubular channel with NO3 anions trapped inside.展开更多
基金National Natural Science Foundation of China(No.21732007,21890721,21821002)Strategic Priority Research Program of the Chinese Academy of Sciences(Grant No.XDB20000000)Program of Shanghai Academic Research Leader。
文摘This paper addresses the problem of the observation of the so-called C-C agostic interactions in cyclopropyl complexes of scandium.Three new cyclopropyl complexes of scandium based on theβ-diketiminato ligand were synthesized including by an intramolecular C-H bond activation reaction in one case.X-ray diffraction analysis revealed distorted cyclopropyl groups in the complexes,and the distortion could be observed in solution as well for one of the complexes thanks to the natural abundance INADEQUATE NMR spectroscopy which showed a markedly reduced J_(C-C)coupling constant.This signature of the C-C agostic interaction was further examined using DFT modelling which,together with NBO calculations,indicated that C-H and C-C agostic interactions are not exclusive but can complement each other,accounting for the distortions.The intramolecular C-H bond activation in the scandium biscyclopropyl complex was investigated by isotopic labeling experiments,which indicated a direct proton abstraction of the isopropyl group in theβ-diketiminato ligand by a cyclopropyl group.
基金supported by the Natural Science Foundation of Zhejiang Province(Y5080308)
文摘By employing functional ligand 3,6-bis（3,5-dimethyl-lH-pyrazol-4-yl）-9-methyl- 9H-carbazole, a novel luminescent Ni complex has been obtained. Its structure was characterized by single-crystal X-ray diffraction analysis. Crystal data： monoclinic, space group P2/c, a = 13.4224（18）, b = 13.759（2）, c = 8.0633（17）/~, fl = 96.448（3）~, C23H23NsNi（NO3）2, M,. = 552.19, V = 1479.7（4） A3, Z = 2, Dc = 1.239 g/cm3,/ffMoKa） = 0.700 mm-1, F（000） = 572, the final R = 0.0566 and wR = 0.1336 for 1638 observed reflections with I 〉 2a（/）. X-ray analysis indicates that each metal center coordinates with two N and two H atoms in tetrahedral interaction geometry. Weak interaction between Ni and N atom of pyrazole ligand and agostic bond （Ni...H-N interaction） play important roles in the formation of the 2-dimension framework. Significantly, this framework could pack into a tubular channel with NO3 anions trapped inside.
