A controlled NO-releasing compound: synthesis, molecular structure, spectroscopy, electrochemistry, and chemical reactivity of R,R,S,S-trans-[RuCl(NO)(cyclam)]2+(1,4,8,11-tetraazacyclotetradecane).
A controlled NO-releasing compound: synthesis, molecular structure, spectroscopy, electrochemistry, and chemical reactivity of R,R,S,S-trans-[RuCl(NO)(cyclam)]2+(1,4,8,11-tetraazacyclotetradecane).
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一种受控释放 NO 的化合物：R,R,S,S-反式-[RuCl(NO)(cyclam)]2 (1,4,8,11-四氮杂环十四烷)的合成、分子结构、光谱、电化学和化学反应性
DOI：
10.1021/ic9912979
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发表时间：
2000
影响因子：
4.6
通讯作者：
Clarke,MJ
中科院分区：
文献类型：
--
作者：
Lang,DR;Davis,JA;Lopes,LG;Ferro,AA;Vasconcellos,LC;Franco,DW;Tfouni,E;Wieraszko,A;Clarke,MJ
trans-[RuCl(NO)(cyclam)]2+（cyclam = 1,4,8,11-四氮杂环十四烷）的合成可以通过在K2[RuCl5NO]上加入cyclam或在trans-[RuCl(CF3SO3)(cyclam)]（CF3SO3）上加入NO来完成。trans-[RuCl(NO)(cyclam)](ClO4)2晶体在单斜空间群pp21 /c中形成，单晶胞参数为a= 7.66500(2) Å，b= 24.7244(1) Å，c= 16.2871(2) Å， β = 95.2550（10）°，z = 4。单细胞中两个独立分子中的一个无序地位于对称中心。对于一般位置的离子，Ru−N和N−O键距离和[Ru−N−O]3+键角分别为1.747(4)Å、1.128(5)Å和178.0(4)°。在这两个离子中，cyclam均采用（R，R，S，S）构型，这也与水溶液中二维COSY1H NMR研究结果一致。还原（E°=−0.1 V）导致cl -通过一级动力学（k= 1.5 s-1）快速损失，NO的损失较慢（k= 6.10 × 10-4s-1， ΔH⧧= 15.3 kcal mol-1， ΔS⧧=−21.8 cal mol-1）。由于还原后一氧化氮的缓慢释放，使得estraans -[RuCl(NO)(cyclam)]2+成为一种有前景的用于血管舒张等目的的控释一氧化氮前药。与相关的复合物-[Ru(NO)(NH3)4(P(OEt)3)](PF6)2不同，反式-[RuCl(NO)(cyclam)] cl2对小鼠海马片记录的诱发电位无调节作用，可能是因为还原后NO的解离较慢。
The synthesis oftrans-[RuCl(NO)(cyclam)]2+(cyclam = 1,4,8,11-tetraazacyclotetradecane) can be accomplished by either the addition of cyclam to K2[RuCl5NO] or by the addition of NO totrans-[RuCl(CF3SO3)(cyclam)](CF3SO3). Crystals oftrans-[RuCl(NO)(cyclam)](ClO4)2form in the monoclinic space groupP21/c, with unit cell parameters ofa= 7.66500(2) Å,b= 24.7244(1) Å,c= 16.2871(2) Å, β = 95.2550(10)°, andZ= 4. One of the two independent molecules in the unit cell lies disordered on a center of symmetry. For the ion in the general position, the Ru−N and N−O bond distances and the [Ru−N−O]3+bond angle are 1.747(4) Å, 1.128(5) Å, 178.0(4)°, respectively. In both ions, cyclam adopts the (R,R,S,S) configuration, which is also consistent with 2D COSY1H NMR studies in aqueous solution. Reduction (E° = −0.1 V) results in the rapid loss of Cl-by first-order kinetics withk= 1.5 s-1and the slower loss of NO (k= 6.10 × 10-4s-1, ΔH⧧= 15.3 kcal mol-1, ΔS⧧= −21.8 cal mol-1K-1). The slow release of NO following reduction causestrans-[RuCl(NO)(cyclam)]2+to be a promising controlled-release NO prodrug for vasodilation and other purposes. Unlike the related complextrans-[Ru(NO)(NH3)4(P(OEt)3)](PF6)2,trans-[RuCl(NO)(cyclam)]Cl2is inactive in modulating evoked potentials recorded from mice hippocampal slices probably because of the slower dissociation of NO following reduction.