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钌(II)和钌(III)与N7配位嘌呤核苷的反式吡啶四胺配合物。

Trans-pyridine tetraammine complexes of RuII and RuIII with N7-coordinated purine nucleosides.

作者信息

Zhao M, Clarke M J

机构信息

Merkert Chemistry Center, Boston College, Chestnut Hill, MA 02467, USA.

出版信息

J Biol Inorg Chem. 1999 Jun;4(3):318-24. doi: 10.1007/s007750050318.

Abstract

The synthesis, spectroscopic, and electrochemical properties of trans-[L(Pyr)(NH3)4RuII/III] (Pyr = py, 3-phpy, 4-phpy, 3-pnpy, or 4-bnpy; L = H2O, Guo, dGuo, 1MeGuo, Gua, Ino, or G7-DNA) are reported. As expected, the Pyr ligand slows DNA binding by trans-[(H2O)(Pyr)(NH3)4RuII]2+ relative to [(H2O)(NH3)5RuII]2+ and favors reduction of RuIII by about 150 mV. The pyridine ligand also promotes the disproportionation of RuIII to afford the corresponding complexes of RuII and, presumably, RuIV. For L = Ino, disproportionation follows the rate law: d[RuII]/dt = k0[RuIII] + k1[OH-][RuIII], k0 = (2.7 +/- 0.7) x 10(-4) s-1 and k1 = 70 +/- 1 M-1 s-1.

摘要

报道了反式-[L(Pyr)(NH₃)₄RuII/III](Pyr = 吡啶、3-苯基吡啶、4-苯基吡啶、3-吡啶基丙胺或4-苄基吡啶;L = 水、鸟嘌呤、脱氧鸟嘌呤、1-甲基鸟嘌呤、鸟苷、次黄嘌呤或G7-DNA)的合成、光谱和电化学性质。正如预期的那样,相对于[(H₂O)(NH₃)₅RuII]²⁺,Pyr配体减缓了反式-[(H₂O)(Pyr)(NH₃)₄RuII]²⁺与DNA的结合,并使RuIII的还原电位降低约150 mV。吡啶配体还促进RuIII的歧化反应,生成相应的RuII配合物,可能还有RuIV配合物。对于L = 次黄嘌呤,歧化反应遵循速率定律:d[RuII]/dt = k₀[RuIII] + k₁[OH⁻][RuIII],k₀ = (2.7 ± 0.7) × 10⁻⁴ s⁻¹,k₁ = 70 ± 1 M⁻¹ s⁻¹。

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