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- Title
New Members of a Class of Monomeric {Fe(NO)<sub>2</sub>}<sup>10</sup> Dinitrosyliron Complexes and a Dimeric {Fe(NO)<sub>2</sub>}<sup>10</sup>-{Fe(NO)<sub>2</sub>}<sup>10</sup> Dinitrosyliron Complex.
- Authors
Lo, Feng‐Chun; Ho, Yi‐Chieh; Chang, Po‐Ya; Lee, Gene‐Hsiang; Kuo, Ting‐Shen; Chen, Jeng‐Lung; Chen, Chien‐Hong
- Abstract
The monomeric {Fe(NO)2}10 dinitrosyliron complexes (DNICs) [K-18-crown-6-ether][(NO)2Fe(NC9H6-NH)] ( 1), [K-18-crown-6-ether][(NO)2Fe(NC9H6-O)] ( 2), and [K-18-crown-6-ether][(NO)2Fe(NC9H6-S)] ( 3) containing [N,NH], [N,O], and [N,S] ligations were synthesized by displacing the N, N, N′, N′-tetramethylethylenediamine (tmeda) group of {Fe(NO)2}10 (tmeda)Fe(NO)2 with quinolin-8-amide, quinolin-8-olate, and quinolin-8-thiolate, respectively. Anionic {Fe(NO)2}10 DNICs 1- 3 were characterized by IR, 1H NMR, and UV/Vis spectroscopy and single-crystal X-ray diffraction. The binding affinity of the ligands (i.e., [NC9H6NH]-, [NC9H6O]-, and [NC9H6S]-) toward the {Fe(NO)2}10 fragment was also investigated, and ligand substitution was found to follow the order [NC9H6S]- > [NC9H6O]- > [NC9H6NH]-. Displacement of the tmeda group of (tmeda)Fe(NO)2 by [K-18-crown-6-ether][SC6H4- o-NH2] and [PPh4][SC6H4- o-NH2] afforded monomeric {Fe(NO)2}10 DNIC [K-18-crown-6-ether][(NO)2Fe(SC6H4- o-NH2)] ( 4) and dimeric {Fe(NO)2}10-{Fe(NO)2}10 DNIC [PPh4]2[(NO)2Fe(μ-SC6H4- o-NH2)]2 ( 5), respectively. The function of the countercation in the formation of monomeric {Fe(NO)2}10 DNIC 4 or dimeric {Fe(NO)2}10-{Fe(NO)2}10 DNIC 5 was also demonstrated upon reduction of the {Fe(NO)2}9 DNICs [cation][(NO)2Fe(SC6H4- o-NH2)2] ( 6) {cation = K-18-crown-6-ether ( 6a), [PPh4] ( 6b)}. In contrast to the formation of thiolate-containing {Fe(NO)2}9 DNICs through nucleophilic cleavage of the bridging thiolates of Roussin's red esters, the transformation of complexes 4 and 5 into complexes 6a and 6b, respectively, in the presence of disulfide provides a new synthetic pathway for the synthesis of thiolate-containing {Fe(NO)2}9 DNICs.
- Subjects
MONOMERS; ETHER (Anesthetic); QUINOLINE derivatives; AMIDE derivatives; LIGANDS (Chemistry)
- Publication
European Journal of Inorganic Chemistry, 2014, Vol 2014, Issue 22, p3499
- ISSN
1434-1948
- Publication type
Article
- DOI
10.1002/ejic.201402370