Synthesis of phosphite complexes of ruthenium(II)

Selective Photolabilization in trans-[Ru(NH3)4(P(III))H2O]2+ and trans-[Ru(NH3)4(P(OR)3)2]2+ Complexes (P(III) = P(OR)3, P(R)3)

“… Therefore, the solutions employed to measure phosphite photoaquation were adjusted to C H + ≥ 10 -3 M to avoid the thermal back-reaction of phosphite. As judged from the electronic and voltammetric spectra, in acidic solutions ( C H + > 10 -4 M) protected from light, the trans -[Ru(NH 3 ) 4 (P(III))H 2 O] 2+ complex ions do not exhibit any evidence of decomposition on a time scale of weeks. − ,, …”

“…Syntheses. [Ru(NH 3 ) 5 Cl]Cl 2 , [Ru(NH 3 ) 5 H 2 O](PF 6 ) 2 , and trans -[Ru(NH 3 ) 4 (P(OR) 3 ) 2 ](PF 6 ) 2 (R = CH 3 , C 2 H 5 , i C 3 H 7 , C 4 H 9 , t C 4 H 9 , C 2 H 4 Cl, C 6 H 12 N 3 ) were synthesized and characterized according to literature procedures. − trans -[Ru(NH 3 ) 4 (P(III))H 2 O](PF 6 ) 2 were generated in solution from the corresponding trans -[Ru(NH 3 ) 4 (P(III)) 2 ])PF 6 ) 2 salt by dissolving a known amount of the solid in 1.0 × 10 -3 M trifluoroacetic acid solution.…”

“…The electronic spectra in solution of the trans -[Ru(NH 3 ) 4 (P(III)) 2 ] 2+ and trans -[Ru(NH 3 ) 4 (P(III))H 2 O] 2+ complexes, P(III) = P(OR) 3 , P(R) 3 , exhibit well-defined , ligand field bands (LF), without the interference of intraligand (IL) or metal-to-ligand charge transfer (MLCT) absorption.…”

“…Although inert with respect to substitution reactions, owing to the strong Ru(II)→P(III) back-bonding − interaction in such complexes, the Ru(II) center is also quite resistant to oxidation, making the internal conversion from LF states to CTTS states more difficult. Therefore, this class of compounds offers a unique opportunity to study the ligand field excited state photochemistry without complications due to redox or secondary thermal reactions.…”

Nitrosilos complexos de rutênio. Equilíbrio químico, envolvimento em sistemas vegetais e citotoxicidade em modelos de câncer

“…A coordenação de ligantes tipo P(OR) 3 (R = metil, etil, butil, propil e isopropil) a complexos metálicos foi e continua sendo bastante estudada tanto em relação à sua reatividade química quanto às implicações em modelos biológicos (26,30,31,119,124) . As tetraaminas de Ru(II) e Ru(III) são um importante grupo dentre estes compostos (26,119,(131)(132)(133)(134)(135) . Em reações envolvendo complexos tipo trans- preenchidos, favoráveis às ligações do tipo , e orbitais 3d π vazios, disponíveis para retro-doação, o que confere a esses ligantes caráter bifílico (136) , ou seja, eles podem atuar tanto como bases-, assim como ácidos-π.…”