Accessing sodium ferrate complexes containing neutral and anionic N-heterocyclic carbene ligands: structural, synthetic, and magnetic insights

Inorganic Chemistry
Lewis C H MaddockEva Hevia

Abstract

This study reports the synthesis and single-crystal X-ray crystallographic, NMR spectroscopic, and magnetic characterization of a series of sodium ferrates using bis(amide) Fe(HMDS)2 as a precursor (HMDS = 1,1,1,3,3,3-hexamethyldisilazide). Reaction with sodium reagents NaHMDS and NaCH2SiMe3 in hexane afforded donor-solvent-free sodium ferrates [{NaFe(HMDS)3}∞] (1) and [{NaFe(HMDS)2(CH2SiMe3)}∞] (2), respectively, which exhibit contacted ion pair structures, giving rise to new polymeric chain arrangements made up of a combination of inter- and intramolecular Na···Me(HMDS) electrostatic interactions. Addition of the unsaturated NHC IPr (IPr = 1,3-bis(2,6-diisopropylphenyl)imidazol-2-ylidene) to 1 and 2 caused deaggregation of their polymeric structures to form discrete NHC-stabilized solvent-separated ion pairs [Na(IPr)2](+)[Fe(HMDS)3](-) (3) and [(THF)3·NaIPr](+)[Fe(HMDS)2CH2SiMe3](-) (4), where in both cases, the NHC ligand coordinates preferentially to Na. In contrast, when IPr is sequentially reacted with the single-metal reagents NaCH2SiMe3 and Fe(HMDS)2, the novel heteroleptic ferrate (THF)3Na[:C{[N(2,6-(i)Pr2C6H3)]2CHCFe(HMDS)2}] (5) is obtained. This contains an anionic NHC ligand acting as an unsymmetrical bridge betwee...Continue Reading

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Citations

May 10, 2017·Dalton Transactions : an International Journal of Inorganic Chemistry·Lewis C H MaddockEva Hevia
Feb 25, 2017·Angewandte Chemie·Tim N GieshoffAxel Jacobi von Wangelin
Jan 23, 2020·Chemical Communications : Chem Comm·Dennis RottschäferRajendra S Ghadwal
Jan 26, 2020·Chemistry : a European Journal·Kieren J Evans, Stephen M Mansell
Feb 8, 2018·Chemical Communications : Chem Comm·Marina Uzelac, Eva Hevia
Mar 28, 2020·Chemistry : a European Journal·Rajendra GhadwalHans-Georg Stammler

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