Reactivity of a sterically hindered Fe(II) thiolate dimer with amines and hydrazines.
The sterically hindered Fe(II) thiolate dimer Fe(2)(mu-STriph)(2)(STriph)(2) (1; [STriph](-) = 2,4,6-triphenylbenzenethiolate) reacts with primary amines ((t)BuNH(2), aniline) and N(2)H(4) to form the structurally characterized addition complexes Fe(STriph)(2)(NH(2)(t)Bu)(2), Fe(2)(mu-STriph)(2)(STriph)(2)(NH(2)Ph)(2), and Fe(2)(mu-eta(1):eta(1)-N(2)H(4))(2)(N(2)H(4))(4)(STriph)(4) in high yield. Chemical and NMR spectroscopic evidence indicate that the binding of these nitrogen donors is labile in solution and multispecies equilibria are likely. With arylhydrazines, 1 catalytically disproportionates 1,2-diphenylhydrazine to aniline and azobenzene, and it rearranges 1-methyl-1,2-diarylhydrazines to give, after treatment with alumina, mononuclear, trigonal bipyramidal Fe(III) complexes of composition Fe(ISQ)(2)(STriph), where [ISQ](-) denotes an appropriately substituted bidentate o-diiminobenzosemiquinonate ligand. Complex 1 shows no reaction with hindered 1,2-dialkylhydrazines (isopropyl or tert-butyl) or tetrasubstituted 1,2-dimethyl-1,2-diphenylhydrazine.
Zdilla
Michael J
MJ
Department of Chemistry, Princeton University, Princeton, New Jersey 08544, USA.
Verma
Atul K
AK
Lee
Sonny C
SC
D000588:Amines / Q000737:chemistry*; D019281:Dimerization; D005296:Ferrous Compounds / Q000737:chemistry*; D006834:Hydrazines / Q000737:chemistry*; D009682:Magnetic Resonance Spectroscopy; D011108:Polymers / Q000737:chemistry; D013440:Sulfides / Q000737:chemistry
D000588:Amines; D005296:Ferrous Compounds; D006834:Hydrazines; D011108:Polymers; D013440:Sulfides; C539579:bis(mu-2,4,6-triphenylbenzenethiolate)bis(2,4,6-triphenylbenzenethiolate)diiron(II); C029424:hydrazine