1246445-36-2Relevant academic research and scientific papers
A {Fe(NO)3}10 trinitrosyliron complex stabilized by an N-heterocyclic carbene and the cationic and neutral {Fe(NO)2} 9/10 products of its NO release
Hsieh, Chung-Hung,Darensbourg, Marcetta Y.
, p. 14118 - 14125 (2010)
In contrast to the instability of XFe(NO)3 and [R 3PFe(NO)3]+, the N-heterocyclic carbene (NHC)-containing trinitrosyliron complex (TNIC) [(IMes)Fe(NO) 3][BF4] (1) [IMes =1,3-bis(2,4,6-trimethylphenyl)imidazol- 2-ylidene] can be readily isolated and manipulated in solution under ambient conditions. Nevertheless, in the presence of thiolates (SR-), this EPR-silent TNIC (denoted {Fe(NO)3}10 in the Enemark-Feltham notation) releases gaseous NO, affording in the case of SR - = SPh- the EPR-active, neutral dinitrosyliron complex (DNIC) (IMes)Fe(SPh)(NO)2 (3, {Fe(NO)2}9). Carbon monoxide enforces a bimolecular reductive elimination of PhSSPh from 3, yielding (IMes)(CO)Fe(NO)2 (2), a reduced {Fe(NO)2} 10 DNIC. The NO released from TNIC 1 in the presence of SPh - could be taken up by the NO-trapping agent [(bme-dach)Fe] 2 [bme-dach = N,N′-bis(2-mercaptoethyl)-1,4-diazacycloheptane] to form the mononitrosyliron complex (MNIC) (bme-dach)Fe(NO). In the absence of SPh-, direct mixing of [(bme-dach)Fe]2 with 1 releases both NO and the NHC with formation of a spin-coupled, diamagnetic {Fe(NO)} 7-{Fe(NO)2}9 complex, [(NO)Fe(bme-dach)Fe(NO) 2][BF4] (4). In 4, the MNIC serves as a bidentate metallodithiolate ligand of Fe(NO)2, forming a butterfly complex in which the Fe-Fe distance is 2.7857(8) A. Thus, 1 is found to be a reliable synthon for [{Fe(NO)2}9]+. The solid-state molecular structures of complexes 1-3 show that all three complexes have a tetrahedral geometry in which the bulky mesitylene substituents of the carbene ligand appear to umbrella the Fe(NO)2L [L = NO (1), CO (2), SPh (3)] motif.
Synthesis, characterization, and fiber-optic infrared reflectance spectroelectrochemical studies of some dinitrosyl iron diphosphine complexes Fe(NO)2L2 (L = P(C6H4X)3)
Jones, Myron W.,Powell, Douglas R.,Richter-Addo, George B.
, p. 63 - 74 (2014/02/14)
A series of iron dinitrosyl complexes of the form Fe(NO) 2(P(C6H4X)3)2 (X = p-OMe (1), p-Me (2), m-Me (3), p-H (4), p-F (5), p-Cl (6), p-CF3 (7)) has been prepared from the reactions of Fe(NO)2(CO)2 and the respective triarylphosphines. Complexes 1-7 have been characterized by IR and 31P NMR spectroscopy, and by X-ray crystallography for 1 and 7. In general, the compounds with the more basic phosphines display lower υNO stretches in the IR spectra than those with the less basic phosphines, and the trends in υNO as a function of Hammett parameter and solvent donor/acceptor number were analyzed. The redox behavior of compounds 1-7 in CH2Cl2 were studied by cyclic voltammetry at a Pt electrode. In general, the compounds undergo one-electron oxidations. Infrared spectroelectrochemistry revealed that the oxidations generate the derivatives with υNOs that are ～100 cm -1 higher in energy indicative of Fe(NO)2-centered oxidations.
