Ebel Martin, Rehder Dieter
Department of Chemistry, University of Hamburg, D-20146 Hamburg, Germany.
Inorg Chem. 2006 Sep 4;45(18):7083-90. doi: 10.1021/ic0602953.
Reaction of vanadyl sulfate with an aldehyde (2-hydroxy-1-naphthaldehyde (nap); 3-methoxysalicylaldehyde = o-vanillin (van)) and an amino acid carrying an OH group (L-tyrosine (L-tyr); L-serine (L-ser), L-threonine (L-thr)) yielded the complexes [VO(nap-D-Tyr)(H2O)] 1a, [VO(van-D,L-Tyr)(H2O)] 1c, [VO(nap-Ser)(H2O)] 2a, [VO(van-D,L-Ser)(H2O)] 2b, [VO(nap-Thr)(H2O)] 3a, and [VO(van-Thr)(H2O)] 3b. [VO(nap-L-tyr(H2O)], 1b, was obtained from the reaction between [VO(nap)(2)] and l-TyrOMe. The crystal and molecular structures of 1a.CH3OH, 1b.CH3OH, 1c.H2O, 2b.2H2O, and the Schiff base nap-D,L-TyrOMe (4) are reported. The ligands coordinate in a tridentate manner through the phenolate component of nap or van, the imine nitrogen, and the carboxylate of the amino acid. Direct coordination of the (deprotonated) OH amino acid functionality is not observed in these complexes. Instead, the OH groups are involved in hydrogen bonding, leading, along with pi-pi stacking, to extended one- and three-dimensional supramolecular networks. The relevance for the interaction between oxovanadium(IV,V) and proteins having serine, threonine, or tyrosine at their reactive sites is addressed.
硫酸氧钒与醛（2-羟基-1-萘甲醛（nap）；3-甲氧基水杨醛 = 邻香草醛（van））以及带有羟基的氨基酸（L-酪氨酸（L-tyr）；L-丝氨酸（L-ser），L-苏氨酸（L-thr））反应生成了配合物[VO(nap-D-Tyr)(H₂O)] 1a、[VO(van-D,L-Tyr)(H₂O)] 1c、[VO(nap-Ser)(H₂O)] 2a、[VO(van-D,L-Ser)(H₂O)] 2b、[VO(nap-Thr)(H₂O)] 3a和[VO(van-Thr)(H₂O)] 3b。[VO(nap-L-tyr(H₂O)]，1b，是由[VO(nap)(2)]与L-TyrOMe反应得到的。报道了1a·CH₃OH、1b·CH₃OH、1c·H₂O、2b·2H₂O以及席夫碱nap-D,L-TyrOMe（4）的晶体和分子结构。配体通过nap或van的酚盐部分、亚胺氮以及氨基酸的羧酸盐以三齿方式配位。在这些配合物中未观察到（去质子化的）OH氨基酸官能团的直接配位。相反，OH基团参与氢键作用，与π-π堆积一起导致形成扩展的一维和三维超分子网络。探讨了氧钒（IV,V）与在其反应位点含有丝氨酸、苏氨酸或酪氨酸的蛋白质之间相互作用的相关性。
