253150-42-4Relevant articles and documents
Iron-mediated hydrazine reduction and the formation of iron-arylimide heterocubanes
Zdilla, Michael J.,Verma, Atul K.,Lee, Sonny C.
, p. 1551 - 1562 (2011)
The reaction of Fe(N{SiMe3}2)2 (1) with 1 equiv of arylthiol (ArSH) results in material of notional composition Fe(SAr)(N{SiMe3}2) (2), from which crystalline Fe 2(μ-SAr)2(N{SiMe3}2) 2(THF)2 (Ar = Mes) can be isolated from tetrahydrofuran (THF) solvent. Treatment of 2 with 0.5 equiv of 1,2-diarylhydrazine (Ar?NH-NHAr?, Ar? = Ph, p-Tol) yields ferric-imide-thiolate cubanes Fe 4(μ3-NAr?)4(SAr)4 (3). The site-differentiated, 1-electron reduced iron-imide cubane derivative [Fe(THF)6][Fe4(μ3-N-p-Tol) 4(SDMP)3(N{SiMe3}2)]2 ([Fe(THF)6][4]2; DMP = 2,6-dimethylphenyl) can be isolated by adjusting the reaction stoichiometry of 1/ArSH/Ar?NHNHAr? to 9:6:5. The isolated compounds were characterized by a combination of structural (X-ray diffraction), spectroscopic (NMR, UV-vis, Moessbauer, EPR), and magnetochemical methods. Reactions with a range of hydrazines reveal complex chemical behavior that includes not only N-N bond reduction for 1,2-di- and trisubstituted arylhydrazines, but also catalytic disproportionation for 1,2-diarylhydrazines, N-C bond cleavage for 1,2-diisopropylhydrazine, and no reaction for hindered and tetrasubstituted hydrazines.
