Mechanism of formation of iron(II) complexes with pentadentate ligands via C-C bond formation between trans-[Fe(2,4-bis(2-pyridylmethylimino)pentane)(MeCN)2]ClO4]2.MeCN and various nitriles.
The order of relative reactivity of nitriles for the formation of Fe(II) complexes (2s) with 3-(1-alkyl(or aryl)methyl)-1-imino-2,4-bis(2-pyridylmethylimine)(L(2)s) from that with 2,4-bis(2-pyridylmethylimono)pentane (L1), trans-[FeL(1)(MeCN)(2)][ClO(4)](2).MeCN (1), and various nitriles has been determined based on the following order: C(6)F(5)CN > 3,4-difluorobenzonitrile > 4-fluorobenzonitrile > C(6)H(5)CN > C(6)H(5)CH(2)CN > C(2)H(5)CN > MeCN > Me(2)CHCN >>Me(3)CN. An iron(II) complex with L1 in a cis-configuration was prepared as the ternary complex [FeL(1)(bpy)][ClO(4)](2).1.5MeNO(2).0.5H(2)O, 3a (bpy = bipyridine). Compounds 2s and 3a undergo enantiomeric interconversion with an activation energy of ca. 60 kJ mol(-1).
Kurosaki
Hiromasa
H
Graduate School of Pharmaceutical Sciences, Kumamoto University, 5-1 Oe-honmachi, Kumamoto 862-0973, Japan. ayasaya@gpo.kumamoto-u.ac.jp
Ishikawa
Yoshinobu
Y
Ishihara
Takao
T
Yamamoto
Teruo
T
Yamaguchi
Yoshihiro
Y
Goto
Masafumi
M
D005296:Ferrous Compounds / Q000138:chemical synthesis* / Q000737:chemistry; D008024:Ligands; D009682:Magnetic Resonance Spectroscopy / Q000379:methods / Q000592:standards; D008958:Models, Molecular; D008968:Molecular Conformation; D009570:Nitriles / Q000737:chemistry*; D012015:Reference Standards; D013237:Stereoisomerism
C516256:(2,4-bis(2-pyridylmethylimino)pentane)bis(acetonitrile)iron(II); D005296:Ferrous Compounds; D008024:Ligands; D009570:Nitriles