TY - JOUR
T1 - Preparation, structure, and properties of tetranuclear vanadium(III) and (IV) complexes bridged by diphenyl phosphate or phosphate
AU - Sato, Kyouhei
AU - Ohnuki, Tetsuya
AU - Takahashi, Haruka
AU - Miyashita, Yoshitaro
AU - Nozaki, Koichi
AU - Kanamori, Kan
PY - 2012/5/7
Y1 - 2012/5/7
N2 - Three novel tetranuclear vanadium(III) or (IV) complexes bridged by diphenyl phosphate or phosphate were prepared and their structures characterized by X-ray crystallography. The novel complexes are [{V(III) 2(μ- hpnbpda)} 2{μ-(C 6H 5O) 2PO 2} 2(μ-O) 2]•6CH 3OH (1), [{V(III) 2(μ-tphpn)(μ-η 3-HPO 4)} 2(μ-η 4-PO 4)](ClO 4) 3•4.5H 2O (2), and [{(V(IV)O) 2(μ-tphpn)} 2(μ-η 4-PO 4)](ClO 4) 3•H 2O (3), where hpnbpda and tphpn are alkoxo-bridging dinucleating ligands. H 3hpnbpda represents 2-hydroxypropane-1,3-diamino-N,N′-bis(2-pyridylmethyl)-N, N′-diacetic acid, and Htphpn represents N,N,N′,N′-tetrakis(2- pyridylmethyl)-2-hydroxy-1,3-propanediamine. A dinuclear vanadium(IV) complex without a phosphate bridge, [(VO) 2(μ-tphpn)(H 2O) 2](ClO 4) 3•2H 2O (4), was also prepared and structurally characterized for comparison. The vanadium(III) center in 1 adopts a hexacoordinate structure while that in 2 adopts a heptacoordinate structure. In 1, the two dinuclear vanadium(III) units bridged by the alkoxo group of hpnbpda are further linked by two diphenylphosphato and two oxo groups, resulting in a dimer-of-dimers. In 2, the two vanadium(III) units bridged by tphpn are further bridged by three phosphate ions with two different coordination modes. Complex 2 is oxidized in aerobic solution to yield complex 3, in which two of the three phosphate groups in 2 are substituted by oxo groups.
AB - Three novel tetranuclear vanadium(III) or (IV) complexes bridged by diphenyl phosphate or phosphate were prepared and their structures characterized by X-ray crystallography. The novel complexes are [{V(III) 2(μ- hpnbpda)} 2{μ-(C 6H 5O) 2PO 2} 2(μ-O) 2]•6CH 3OH (1), [{V(III) 2(μ-tphpn)(μ-η 3-HPO 4)} 2(μ-η 4-PO 4)](ClO 4) 3•4.5H 2O (2), and [{(V(IV)O) 2(μ-tphpn)} 2(μ-η 4-PO 4)](ClO 4) 3•H 2O (3), where hpnbpda and tphpn are alkoxo-bridging dinucleating ligands. H 3hpnbpda represents 2-hydroxypropane-1,3-diamino-N,N′-bis(2-pyridylmethyl)-N, N′-diacetic acid, and Htphpn represents N,N,N′,N′-tetrakis(2- pyridylmethyl)-2-hydroxy-1,3-propanediamine. A dinuclear vanadium(IV) complex without a phosphate bridge, [(VO) 2(μ-tphpn)(H 2O) 2](ClO 4) 3•2H 2O (4), was also prepared and structurally characterized for comparison. The vanadium(III) center in 1 adopts a hexacoordinate structure while that in 2 adopts a heptacoordinate structure. In 1, the two dinuclear vanadium(III) units bridged by the alkoxo group of hpnbpda are further linked by two diphenylphosphato and two oxo groups, resulting in a dimer-of-dimers. In 2, the two vanadium(III) units bridged by tphpn are further bridged by three phosphate ions with two different coordination modes. Complex 2 is oxidized in aerobic solution to yield complex 3, in which two of the three phosphate groups in 2 are substituted by oxo groups.
UR - http://www.scopus.com/inward/record.url?scp=84860675037&partnerID=8YFLogxK
U2 - 10.1021/ic2024617
DO - 10.1021/ic2024617
M3 - 学術論文
C2 - 22486192
AN - SCOPUS:84860675037
SN - 0020-1669
VL - 51
SP - 5026
EP - 5036
JO - Inorganic Chemistry
JF - Inorganic Chemistry
IS - 9
ER -