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

Abstract

Neste trabalho foi investigado o ataque nucleofílico sofrido no estado sólido pelo complexo trans- [Ru(NO)

The chemistry of Group 8 metal complexes with phosphinous acids and related P OH ligands

“…ligand in trans-[Ru(NO)(NH3)4{P(OEt)3}][PF6]3, a reaction that was found to occur both in aqueous solution[50] and in the solid state after prolonged exposure to air[51].Related P-OR hydrolysis processes were also observed in aqueous solution for the trialkylphosphite complexes trans-[Ru(NO)(NH3)4{P(OR)3}][PF6]3 (R = Me, i Pr, n Bu)[50].In the context of their studies on the cooperative heteroatom-hydrogen bonds activation with transition metal carbene complexes[52], Gessner and co-workers studied the reactivity of the nucleophilic ruthenium(II)-carbene derivative 47 towards aromatic SPOs (Scheme 11)[53]. The reactions, performed in toluene at room temperature, resulted in the expected neat addition of the P-H bond of the SPOs across the Ru=C bond of 47, thus allowing the isolation of the novel phosphinito complexes 48.…”

Nitric Oxide and Nitroxyl Products from the Reaction of L‐Cysteine with trans‐[RuNO(NH3)4P(OEt)3](PF6)3

“…As previously reported, [17][18][19][20] the reactions between nitrosyl ruthenium complexes and nucleophilic agents, such as cysteine and glutathione, occur according to the reaction sequences shown in Equations (3) and (4).…”

“…On the basis of the experimental data and information reported in the literature [17][18][19][20]22] for related systems, a nucleophilic attack on the nitrogen by a thiol sulfur atom, such as in the reactions illustrated in Equations (8) and (9) is anticipated. 465 nm and a simultaneous increase in the solution absorbance at 320 nm (Figure 4, A).…”

A importância do estado excitado 3MLCT de compostos de Ru(II), Re(I) e Ir(III) no desenvolvimento de fotossensores, OLEDS e fotorredução de CO2

“…[9][10][11][12][13][14][15][16] Compostos de coordenação apresentam grande potencial para aplicações em sistemas fotoquímicos [17][18][19][20][21][22][23][24][25][26] devido à possibilidade de incorporar diferentes ligantes a centros metálicos para formar subunidades com funcionalidades específicas que podem estar relacionadas às suas transições eletrônicas. 27 Em complexos octaédricos podem ocorrer transições eletrônicas centradas no metal (MC, Metal Centered); Intraligante (IL, IntraLigand); transições de transferência de carga do ligante para o metal (LMCT, Ligand-to-Metal Charge Transfer); e transições de transferência de carga do metal para o ligante (MLCT, Metal-to-Ligand Charge Transfer), Figura 1. O processo fotoquímico, que se inicia com a absorção de luz por uma espécie química e resulta na transição de um elétron do estado fundamental para um estado excitado, pode ter seu mecanismo representado por um diagrama de Jablonski, Figura 2.…”