An iron(II) hydride complex of a ligand with two adjacent beta-diketiminate binding sites and its reactivity
Gehring H, Metzinger R, Braun B, Herwig C, Harder S, Ray K, Limberg C (2016)
Publication Status: Published
Publication Type: Journal article
Publication year: 2016
Journal
Publisher: Royal Society of Chemistry
Book Volume: 45
Pages Range: 2989-2996
Journal Issue: 7
DOI: 10.1039/c5dt04266f
Abstract
After lithiation of PYR-H-2 (PYR = [(NC(Me)C(H)C(Me)NC6H3(iPr)(2))(2)(C5H3N)](2)(-)) - the precursor of an expanded beta-diketiminato ligand system with two binding pockets -with KN(TMS)(2) the reaction of the resulting potassium salt with FeBr2 led to a dinuclear iron(II) bromide complex [(PYR)Fe(mu-Br)(2)Fe] (1). Through treatment with KHBEt3 the bromide ligands could be replaced by hydrides to yield [PYR) Fe-2(mu-H)(2)] (2), a distorted analogue of known beta-diketiminato iron hydride complexes, as evidenced by NMR, Mossbauer and X-ray absorption spectroscopy, as well as by its reactivity: for instance, 2 reacts with the proton source lutidinium triflate via protonation of the hydride ligands to form an iron(II) product [(PYR)Fe-2(OTf)(2)] (4), while CO2 inserts into the Fe-H bonds generating the formate complex [(PYR) Fe-2(mu-HCOO)(2)] (5); in the presence of traces of water partial hydrolysis occurs so that [(PYR) Fe-2(mu-OH)(mu-HCOO)] (6) is isolated. Altogether, the iron(II) chemistry supported by the PYR2-ligand is distinctly different from the one of nickel(II), where both, the arrangement of the two binding pockets and the additional pyridyl donor led to diverging features as compared with the corresponding system based on the parent beta-diketiminato ligand.
Authors with CRIS profile
Involved external institutions
Germany (DE)How to cite
APA:
Gehring, H., Metzinger, R., Braun, B., Herwig, C., Harder, S., Ray, K., & Limberg, C. (2016). An iron(II) hydride complex of a ligand with two adjacent beta-diketiminate binding sites and its reactivity. Dalton Transactions, 45(7), 2989-2996. https://dx.doi.org/10.1039/c5dt04266f
MLA:
Gehring, Henrike, et al. "An iron(II) hydride complex of a ligand with two adjacent beta-diketiminate binding sites and its reactivity." Dalton Transactions 45.7 (2016): 2989-2996.
BibTeX: Download