Ligand Design for Isomer-Selective Oxorhenium(V) Complex Synthesis
| Autor: | Timothy J. Strathmann, Dimao Wu, Mengwei Han, Jinyong Liu, Charles J. Werth, Xiaoge Su, Danielle L. Gray, John R. Shapley |
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| Rok vydání: | 2017 |
| Předmět: |
Steric effects
chemistry.chemical_classification 010405 organic chemistry Ligand Stereochemistry Crystal structure Dihedral angle 010402 general chemistry 01 natural sciences Medicinal chemistry 0104 chemical sciences Inorganic Chemistry Perchlorate chemistry.chemical_compound chemistry Chelation Physical and Theoretical Chemistry Cis–trans isomerism Alkyl |
| Zdroj: | Inorganic Chemistry. 56:1757-1769 |
| ISSN: | 1520-510X 0020-1669 |
| Popis: | Recently, N,N-trans Re(O)(LN–O)2X (LN–O = 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)(LN–O)2X 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)(LN–O)2Cl complexes. Analysis of the crystal structures revealed that the dihedral angles (DAs) between the two LN–O ligands of N,N-cis Re(O)(LN–O)2Cl complexes are less than 90°, whereas the DAs in most N,N-trans complexes are greater than 90°. Variably sized alkyl groups (−Me, −CH2Ph, and −CH2Cy) 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 forma... |
| Databáze: | OpenAIRE |
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