Iron-mediated hydrazine reduction and the formation of iron-arylimide heterocubanes.
The reaction of Fe(N{SiMe(3)}(2))(2) (1) with 1 equiv of arylthiol (ArSH) results in material of notional composition Fe(SAr)(N{SiMe(3)}(2)) (2), from which crystalline Fe(2)(μ-SAr)(2)(N{SiMe(3)}(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)(μ(3)-NAr')(4)(SAr)(4) (3). The site-differentiated, 1-electron reduced iron-imide cubane derivative [Fe(THF)(6)][Fe(4)(μ(3)-N-p-Tol)(4)(SDMP)(3)(N{SiMe(3)}(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, Mössbauer, 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.
Department of Chemistry, Princeton University, Princeton, New Jersey 08544, United States.
Michael J
MJ
Zdilla
Atul K
AK
Verma
Sonny C
SC
Lee
D002244:Carbon / Q000737:chemistry; D005663:Furans / Q000737:chemistry; D006834:Hydrazines / Q000737:chemistry*; D006844:Hydrocarbons, Cyclic / Q000138:chemical synthesis* / Q000737:chemistry; D007094:Imides / Q000138:chemical synthesis* / Q000737:chemistry; D007501:Iron / Q000737:chemistry*; D008956:Models, Chemical; D009584:Nitrogen / Q000737:chemistry; D009942:Organometallic Compounds / Q000138:chemical synthesis* / Q000737:chemistry; D012997:Solvents / Q000737:chemistry; D013057:Spectrum Analysis; D013438:Sulfhydryl Compounds / Q000737:chemistry; D014961:X-Ray Diffraction
D005663:Furans; D006834:Hydrazines; D006844:Hydrocarbons, Cyclic; D007094:Imides; D009942:Organometallic Compounds; D012997:Solvents; D013438:Sulfhydryl Compounds; C029424:hydrazine; C018674:tetrahydrofuran; D002244:Carbon; D007501:Iron; D009584:Nitrogen