Synthesis, Structure, and Reactivity of (Dihydrogen)(hydrido)iron(II) Complexes Bearing Chiral Diphosphanes
| Autor: | Marta Feliz, Francisco Estevan |
|---|---|
| Rok vydání: | 2015 |
| Předmět: |
Phanes
Stereochemistry Hydrogen molecule 010402 general chemistry 010403 inorganic & nuclear chemistry 01 natural sciences Medicinal chemistry Heterolysis 0104 chemical sciences Inorganic Chemistry chemistry.chemical_compound chemistry Reactivity (chemistry) Enantiomer DuPhos Benzene Cis–trans isomerism |
| Zdroj: | European Journal of Inorganic Chemistry. 2016:92-102 |
| ISSN: | 1099-0682 1434-1948 |
| DOI: | 10.1002/ejic.201501085 |
| Popis: | The heterolytic cleavage of molecular hydrogen by [Fe(H2O)6][BF4]2 and the chiral phosphane (+)-1,2-bis[(2R,5R)-2,5-dimethylphospholano]benzene [(R,R)-Me-DuPhos] or its enantiomer [(S,S)-Me-DuPhos] yields the (dihydrogen)(hydrido)iron complexes [FeH(2-H2){(R,R)-Me-DuPhos}2]BF4 ([R,R-1]BF4) and [FeH(2-H2){(S,S)-Me-DuPhos}2]BF4 ([S,S-1]BF4), respectively. These complexes are fluxional in solution at room temperature, and the trans isomers are observed at 200 K. The ()-cis-[R,R-1]BF4 complex was identified crystallographically as the only stereoisomer at room temperature. The energetic and structural differences between the cis ( and ) and trans isomers were analyzed from a computational (DFT) perspective. The coordinated dihydrogen is displaced by CO or CH3CN ligands to form a mixture of cis and trans isomers of FeH(L)[(R,R)-Me-DuPhos]2BF4 {L = CO ([R,R-2]BF4), CH3CN ([R,R-3]BF4)} or FeH(L)[(S,S)-Me-DuPhos]2BF4 {L = CO ([S,S-2]BF4), CH3CN ([S,S-3]BF4)} complexes, and the cis isomers are the major ones. The formation of trans-[FeH(NMe3)(Me-DuPhos*)2]BF4 is suggested for the reaction of [R,R-1]BF4 and [S,S-1]BF4 with NMe3 {Me-DuPhos* = [(R,R)-Me-DuPhos] or [(S,S)-Me-Duphos]}. |
| Databáze: | OpenAIRE |
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