Reactivity of trans-[Ru(NH3)4P(OEt)3NO]X3 (X = PF6-, CF3COO-):: modulation of the release of NO by the trans-effect

被引:43
作者
Lopes, LGF
Castellano, EE
Ferreira, AG
Davanzo, CU
Clarke, MJ
Franco, DW
机构
[1] Univ Sao Paulo, Inst Quim Sao Carlos, BR-13560970 Sao Carlos, SP, Brazil
[2] Univ Fed Ceara, Dept Quim Organ & Inorgan, BR-60455970 Fortaleza, Ceara, Brazil
[3] Univ Sao Paulo, Inst Fis Sao Carlos, Sao Carlos, SP, Brazil
[4] Univ Fed Sao Carlos, Dept Quim, BR-13560 Sao Carlos, SP, Brazil
[5] Univ Estadual Campinas, Inst Quim, Campinas, SP, Brazil
[6] Boston Coll, Dept Chem, Chestnut Hill, MA 02167 USA
基金
巴西圣保罗研究基金会;
关键词
nitric oxide; NO release; ruthenium complex;
D O I
10.1016/j.ica.2004.07.014
中图分类号
O61 [无机化学];
学科分类号
070301 ; 081704 ;
摘要
The synthesis, characterization and reactivity of trans-[Ru(NH3)(4)P(OEt)(3)NO]X-3 (X = PF6- and CF3COO-) are presented. The X-ray structure of trans-[Ru(NH3)(4)P(OEt)(3)NO](CF3COO)(3) center dot 3CF(3)COOH indicates coordination of the nitrosyl as NO. with a Ru-N-O angle of 175.1(8)degrees and a Ru-NO bond length of 1.774(8) angstrom. Loss of NO2- from trans-[Ru(NH3),P(OEt)(3)NO](3)(+) is pH dependent with k(obs) (S-1) = (k(0)K(a) + k(1)[H+])/([H+] + K-a)], where k(0) = 2 x 10(-5) s(-1), k(1) = 0.40 +/- 0.03 s(-1), and pK(a), = 8.6 +/- 0.3. The nitrosyl complex undergoes a one-electron reduction (E-0 = 0.14 V versus NHE) involving the coordinated nitrosyl group followed by dissociation of NO, which is facilitated by the phosphito ligand (k(-NO) = 0.97 s(-1) at 25 degrees C and pH 5.0). (c) 2004 Published by Elsevier B.V.
引用
收藏
页码:2883 / 2890
页数:8
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