Synthesis and Structures of Vanadium–Cerium Trinuclear Complexes with Schiff-Base Ligands

• Published in: Bulletin of the Chemical Society of Japan Vol. 79; no. 9; pp. 1393 - 1397
• Main Authors: Tsuchimoto, Masanobu, Ishii, Toshio, Imaoka, Takane, Yamamoto, Kimihisa, Yoshioka, Naoki, Sunatsuki, Yukinari
• Format: Journal Article
• Language: English
• Published: TOKYO The Chemical Society of Japan 01.09.2006; Chemical Soc Japan; Chemical Society of Japan
• Subjects: Chemistry; Chemistry, Multidisciplinary; Physical Sciences; Science & Technology; CU; LANTHANIDES; GROUND-STATE; CRYSTAL-STRUCTURES; IONS; MAGNETIC-PROPERTIES; GD
• ISSN: 0009-2673; 1348-0634
• DOI: 10.1246/bcsj.79.1393

A vanadium(V)–cerium(IV) trinuclear complex, [{VVO2(L1)}2CeIV] (1) (H3L1: N,N′-bis-3-ethoxysalicylidene-2-hydroxy-1,3-propanediamine), was prepared by the reaction of [VIVO(acac)2] and [CeIII(acac)3]·3H2O with H3L1 in CH3CN, followed by oxidation of the product in air. The structure of complex 1 was determined by X-ray crystal structure analysis. The complex has a VV–CeIV–VV trinuclear structure with two dioxovanadium(V) moieties on each side of the cerium(IV) moiety. Complex 1 has two L1 ligands to form a trinuclear structure. The basal oxo atoms of the dioxovanadium(V) moieties are coordinated to the cerium atom with Ce–O distances of 2.322(3) and 2.343(3) Å. The apical two non-coordinating oxo atoms are oriented to the same direction to form an endo structure. IR data of complex 1 show V=O stretching bands at 975 cm−1 for the apical non-coordinated oxo atoms and 802 cm−1 for the basal coordinated oxo atoms. The cyclic voltammogram of complex 1 in CH3CN shows a quasi-reversible two-electron redox couple with E1/2 = −0.60 V vs Fc/Fc+.