Synthesis and bonding analysis of pentagonal bipyramidal rhenium carboxamide oxo complexes
Synthesis and bonding analysis of pentagonal bipyramidal rhenium carboxamide oxo complexes
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五角双锥铼甲酰胺氧配合物的合成及成键分析
DOI：
10.1039/d3dt02617e
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发表时间：
2023
影响因子：
4
通讯作者：
Miller, Alexander J.
中科院分区：
文献类型：
--
作者：
McMillion, Noah D.;Bruch, Quinton J.;Chen, Chun-Hsing;Hasanayn, Faraj;Miller, Alexander J.
报道了一种四齿联吡啶酰胺/酰胺配体负载的七配位二氧代配合物。中性二甲酰胺H2 Phbpy-da配体最初以L4（ONNO）方式配位到八面体的二氧代前体，产生七配位二氧代络合物。随后的去质子化产生一个新的氧代配合物，其特征在于配体的双阴离子（L2 X2）羧酰胺（NNNN）形式。计算研究提供了深入了解可能的连接异构体的相对稳定性后去质子化。结构研究和分子轨道理论合理化的相对异构体的稳定性，并提供洞察到的-氧键顺序。
Seven-coordinate rhenium oxo complexes supported by a tetradentate bipyridine carboxamide/carboxamidate ligand are reported. The neutral dicarboxamide H2Phbpy-da ligand initially coordinates in an L4 (ONNO) fashion to an octahedral rhenium oxo precursor, yielding a seven-coordinate rhenium oxo complex. Subsequent deprotonation generates a new oxo complex featuring the dianionic (L2X2) carboxamidate (NNNN) form of the ligand. Computational studies provide insight into the relative stability of possible linkage isomers upon deprotonation. Structural studies and molecular orbital theory are employed to rationalize the relative isomer stability and provide insight into the rhenium–oxo bond order.