Nitric oxide as an activation agent for nucleophilic attack in trans-[Ru(NO)(NH3)4{P(OEt)3}](PF6)3

Journal of the Brazilian Chemical Society

Lima, Francisco C. A.¹  Magalhães, Alvicler¹  Universidade Estadual de Campinas, Campinas, Brazil¹  Cardoso, Daniel R.¹  Toledo Jr., José C.¹  Franco, Douglas W.¹  Metzker, Gustavo¹  Universidade de São Paulo, São Carlos, Brazil¹  Universidade Estadual do Piauí, Teresina, Brazil¹  Universidade Federal do ABC, Santo André, Brazil¹ 

关键词: nitrosyl;    ruthenium;    phosphorus ester;   

DOI  :  10.1590/S0103-50532010000700014

学科分类：化学（综合）

来源: SciELO

【 摘 要 】

The complex trans-[Ru(NO)(NH3)4{P(OEt)3}](PF6)3 undergoes nucleophilic attack on the phosphorus ester ligand in the solid state yielding trans-[Ru(NO)(NH3)4{P(OH)(OEt)2}](PF6)3. The reaction was monitored and the products analyzed using nuclear magnetic resonance spectroscopy (31P{1H} CP-MAS NMR and 31P{1H} NMR), infrared spectroscopy (FTIR), electron paramagnetic resonance spectroscopy (EPR), cyclic voltammetry (CV), electronic spectroscopy (UV-Vis) and elemental analysis. According to experimental data and quantum mechanical calculations (DFT), the reaction proceeds in the solid state by the nucleophilic attack on the phosphorus ligand, promoted by the strong polarization along the PIII–RuII–NO+ axis induced by the nitrosyl ligand, and takes place following the Michaelis-Arbusov type mechanism for phosphorus ester hydrolysis. In solution, the nucleophilic attack occurs simultaneously at the nitrosyl and triethylphosphite ligands, yielding trans-[Ru(H2O)(NH3)4{P(OEt)3}]2+ and trans-[Ru(NO)(H2O)(NH3)4]3+ in comparable amounts.

【 授权许可】

Unknown