A PNNH Pincer Ligand Allows Access to Monovalent Iron

作者:Polezhaev Alexander V.; Liss Cameron J.; Telser Joshua; Chen Chun-Hsing; Caulton Kenneth G.*
来源:Chemistry - A European Journal, 2018, 24(6): 1330-1341.
DOI:10.1002/chem.201703795

摘要

Reaction of the unsymmetrically armed pincer PNNH (phosphine-pyridyl-pyrazole) ligand with FeCl2 yielded the five-coordinate monomer [(PNNH)FeCl2], the NH proton of which captures THF through the formation of a hydrogen bond. Deprotonation of this NH functionality with Li[N(SiMe3)(2)] did not give the four-coordinate [(PNN)FeCl], but instead retained LiCl to yield [(PNNLi)FeCl2], in which the lithium bridges between the pyrazolate beta-nitrogen and one of the chlorides on iron. One-electron reduction of this compound under CO occurred with the loss of LiCl to form the square-pyramidal monovalent iron in [(PNN)Fe(CO)(2)], which was characterized by IR, Mossbauer, and EPR spectroscopy, X-ray diffraction, and DFT calculations. Cyclic voltammetry studies of [(PNN) Fe(CO)(2)] showed a reversible reduction wave and the reduction product was synthesized by using KC8. The product K[(PNN)Fe(CO)(2)] contains saturated, five-coordinate Fe-0; the (PNN) Fe subunit is anionic and the K+ cations cluster close to the pyrazolate side of the two CO ligands. Potassium electrophile complete its coordination sphere through interactions with the oxygen atom of a CO of a neighboring unit, thereby creating a polymeric chain. The reaction of [(PNN)Fe(CO)(2)] with HBpin (4,4,5,5-tetramethyl-1,3,2-dioxaborolane) resulted in the reduction of the metal center (by release of H-2) and borylation of the pyrazole beta-nitrogen atom. This redox-active addition of the H-B bond across the metal-ligand assembly is an unusual example of metal-ligand cooperativity and establishes a ligand that supports iron in three different oxidation states.

  • 出版日期2018-1-26