Article ID | Journal | Published Year | Pages | File Type |
---|---|---|---|---|
1327004 | Journal of Organometallic Chemistry | 2008 | 11 Pages |
The first phosphinooxazoline chelate complexes of iron were synthesized, and their structural and electronic properties were studied.The known phosphinooxazolines 2-(2-(diphenylphosphino)phenyl)-4,5-dihydrooxazole (7a), 2-(2-(diphenylphosphino)phenyl)-4,4-dimethyl-4,5-dihydrooxazole (7b), (S)-4-benzyl-2-(2-(diphenylphosphino)phenyl)-4,5-dihydrooxazole (7e) and (R)-2-(2-(diphenylphosphino)phenyl)-4-phenyl-4,5-dihydrooxazole (7f) were synthesized by a modified three step literature procedure with improved 67–60% overall yields. The new electronically tuned phosphinooxazolines 2-(5-bromo-2-(diphenylphosphino)phenyl)-4,4-dimethyl-4,5-dihydrooxazole (7c), 3-(4,4-dimethyl-4,5-dihydrooxazol-2-yl)-4-(diphenylphosphino)-N,N-dimethylaniline (7d) and 2-(2-(diphenylphosphino)-3-(trifluoromethyl)phenyl)-4,4-dimethyl-4,5-dihydrooxazole (7g) were synthesized in three to six steps with 59–29% overall yields. Reaction of 7a–f with CpFe(CO)2I (110 °C, 2 h, toluene) gave the iodide salts of the new iron phosphinooxazoline complexes [CpFe(CO)(7a–f)]+ in 87–21% yield. The new complexes were characterized by X-ray and the molecular structures confirm the octahedral coordination geometry and the half-sandwich structure about the iron center. The impact of different oxazoline ligands on the steric and electronic properties of their iron complexes was determined by analysis of selected bond lengths, νCO stretching frequency and the oxidation potentials of the ligands and the iron complexes.
Graphical abstractA series of new chelating phosphinooxazoline complexes of iron was synthesized and structurally characterized. Sterically and electronically tuned phosphinooxazoline were employed as ligands, and the impact of the ligand structure on the properties of the corresponding iron complexes was studied by means of IR and cyclic voltammetry.Figure optionsDownload full-size imageDownload as PowerPoint slide