Unusual electronic structure of bis-isocyanide complexes of iron(III) porphyrinoids.
A series of isocyanide complexes, [Fe(Porphyrinoid)((t)BuNC)(2)](+), were synthesized and examined for their physicochemical properties. The molecular structure of the bis((t)BuNC) adduct of the iron(III) porphycene (1) and corrphycene (2) adopting the (d(xy))(2)(d(xz), d(yz))(3) ground state were determined for the first time. Furthermore, 1 and 2 showed unusual crossover phenomena between different electron configurations, (d(xy))(2)(d(xz), d(yz))(3) ground state and (d(xz), d(yz))(4)(d(xy))(1) ground state, by the addition of the external stimuli.
Department of Chemistry, School of Medicine, Toho University, Tokyo, Japan. yohgo@med.toho-u.ac.jp
Yoshiki
Y
Ohgo
Saburo
S
Neya
Daisuke
D
Hashizume
Tomoji
T
Ozeki
Mikio
M
Nakamura
D003486:Cyanides / Q000737:chemistry; D004583:Electrons; D007501:Iron / Q000737:chemistry*; D008665:Metalloporphyrins / Q000138:chemical synthesis / Q000737:chemistry; D008958:Models, Molecular; D011166:Porphyrins / Q000737:chemistry*
D003486:Cyanides; D008665:Metalloporphyrins; D011166:Porphyrins; C540265:corrphycene; C051407:porphycene; D007501:Iron