Ligand Design for Isomer-Selective Oxorhenium(V) Complex Synthesis
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- 作者：Jinyong LiuXiaoge Su ; Mengwei Han ; Dimao Wu ; Danielle L. Gray ; John R. ShapleyCharles J. Werth ; Timothy J. Strathmann
- 刊名：Inorganic Chemistry
- 出版年：2017
- 出版时间：February 6, 2017
- 年：2017
- 卷：56
- 期：3
- 页码：1757-1769
- 全文大小：778K
- ISSN：1520-510X
文摘
Recently, N,N-trans Re(O)(L<sub>N–Osub>)<sub>2sub>X (L<sub>N–Osub> = monoanionic N–O chelates; X = Cl or Br prior to being replaced by solvents or alkoxides) complexes have been found to be superior to the corresponding N,N-cis isomers in the catalytic reduction of perchlorate via oxygen atom transfer. However, reported methods for Re(O)(L<sub>N–Osub>)<sub>2sub>X synthesis often yield only the N,N-cis complex or a mixture of trans and cis isomers. This study reports a geometry-inspired ligand design rationale that selectively yields N,N-trans Re(O)(L<sub>N–Osub>)<sub>2sub>Cl complexes. Analysis of the crystal structures revealed that the dihedral angles (DAs) between the two L<sub>N–Osub> ligands of N,N-cis Re(O)(L<sub>N–Osub>)<sub>2sub>Cl complexes are less than 90°, whereas the DAs in most N,N-trans complexes are greater than 90°. Variably sized alkyl groups (−Me, −CH<sub>2sub>Ph, and −CH<sub>2sub>Cy) were then introduced to the 2-(2′-hydroxyphenyl)-2-oxazoline (Hhoz) ligand to increase steric hindrance in the N,N-cis structure, and it was found that substituents as small as −Me completely eliminate the formation of N,N-cis isomers. The generality of the relationship between N,N-trans/cis isomerism and DAs is further established from a literature survey of 56 crystal structures of Re(O)(L<sub>N–Osub>)<sub>2sub>X, Re(O)(L<sub>O–N–N–Osub>)X, and Tc(O)(L<sub>N–Osub>)<sub>2sub>X congeners. Density functional theory calculations support the general strategy of introducing ligand steric hindrance to favor synthesis of N,N-trans Re(O)(L<sub>N–Osub>)<sub>2sub>X and Tc(O)(L<sub>N–Osub>)<sub>2sub>X complexes. This study demonstrates the promise of applying rational ligand design for isomeric control of metal complex structures, providing a path forward for innovations in a number of catalytic, environmental, and biomedical applications.