SYNTHESIS AND STRUCTURES OF NIOBIUM(V) AND TANTALUM(V) ANALOGS OF AMAVADIN - [M(HIDA)(2)](-) (M=NB-V OR TA-V, H(3)HIDA EQUALS HYDROXYIMINO-DIACETIC ACID) AND [NB(R,R-HIDPA)(2)](-) [H(3)HIDPA=2,2'-(HYDROXYIMINO)-DIPROPIONIC ACID]
Pd. Smith et al., SYNTHESIS AND STRUCTURES OF NIOBIUM(V) AND TANTALUM(V) ANALOGS OF AMAVADIN - [M(HIDA)(2)](-) (M=NB-V OR TA-V, H(3)HIDA EQUALS HYDROXYIMINO-DIACETIC ACID) AND [NB(R,R-HIDPA)(2)](-) [H(3)HIDPA=2,2'-(HYDROXYIMINO)-DIPROPIONIC ACID], Journal of the Chemical Society. Dalton transactions, (4), 1997, pp. 685-691
Reactions of M(OEt)(5) (M = Nb or Ta) with N-hydroxyiminodiacetic acid
(H(3)hida) yielded the complexes [M(hida)(2)](-) (M = Nb 1 or Ta 2).
Single-crystal X-ray diffraction revealed the Same novel eight-co-ordi
nated structure identified for Amavadin, the form is which vanadium(Iv
) is bound in Amanita muscaria mushrooms. 1 This type of structure giv
es rise to chirality at the metal, where 1 and 2 consist of an equimol
ar mixture of the Delta and Lambda helical forms in the crystal lattic
e. The complexes [Nb(R,R-hidpa)(2)](-) 3a and [Nb(R,S-hidpa)(2)](-) 3b
[H(3)hidpa = 2,2'-(hydroxyimino)dipropionic acid] were synthesized vi
a the route used for 1 and 2, and X-ray crystallography confirmed the
presence of the same Amavadin-style geometry. Cyclic voltammetry-in CH
2Cl2 showed that at 254 K 1 and 3a exhibit quasi-reversible reductions
at E(1/2) = -1.22 and -1.35 V (vs. saturated calomel electrode), resp
ectively, whereas 2 displays an irreversible reduction (-1.92 V).