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)

Abstract

Irradiation in the LF bands 1A1 → 1E(1) and 1A1g → 1A2g, 1Eg leads to NH3 photolabilization of trans-[Ru(NH3)4(P(III))H2O]2+ complexes and to NH3 and P(III) photolabilization of trans-[Ru(NH3)4(P(III))2]2+ species. For both series of complexes ΦNH 3 has essentially the same experimental value of 0.34 ± 0.03 mol/einstein. The ΦP(III) values for the bis(phosphane) complexes trans-[Ru(NH3)4(P(III))2]2+ are in the 0.034−0.070 range for P(III) = P(OCH3)3 and P(OC2H4Cl)3. No clear relationship could be established between the cone angle θ of the phosphane or the formal potential E°‘Ru(III)/Ru(II) and the corresponding ΦNH 3 and ΦP(III) data for the complexes studied. The NH3 ligand is selectively photolabilized when the trans-[Ru(NH3)4(P(III))2]2+ and the trans-[Ru(NH3)4(P(III))H2O]2+ species are irradiated with energies corresponding to the 1A1g → 1A2g and 1A1 → 1A2 transitions.

cis- and trans-nitrosyltetraammineruthenium(II). Spectral and electrochemical properties and reactivity

“…The photolysis experiments were performed according to the procedures described previously. 8 The irradiations were carried out by using an Osram 200 W Hg-Xe lamp in an Oriel model 6292 Universal arc-lamp source with an Oriel interference filter (≈10 nm band pass). Photolysis was done in aqueous trifluoracetic acid solutions containing 1.0 × 10 Ϫ3 to 5 × 10 Ϫ4 mol dm Ϫ3 of the ruthenium complex.…”

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

“…Por exemplo, a população do orbital σ M * pode levar a uma reação de fotolabilização devido à alteração na energia de estabilização do campo ligante. [35][36][37][38][39][40] Por outro lado, reações fotorredox são observadas tipicamente ao atingir os estados excitados envolvendo transições de transferência de carga. 41,42 Neste trabalho serão abordados três temas atuais de grande interesse e que estão relacionados diretamente à aplicação das transições de transferência de carga do tipo MLCT de compostos de coordenação de Ru(II), Re(I) e Ir(III).…”

Synthesis and Characterization of New Ammine Ru(II) Complexes Containing P(m-tol)3, P(p-CH3)3 and P(OC5H11)3

“…The chemistry of phosphine and phosphite complexes of Ru(II) and Ru(III) tetraammines has received considerable attention, [1][2][3][4][5][6][7][8][9][10][11] efforts being directed to the understanding of the trans effect and trans influence of these ligands in the thermal [1][2][3][4][5][6][7][8][9][10][11] and photochemical [12][13][14][15][16][17] reactivities of the ruthenium center the complex itself. According to the accumulated data, [1][2][3][4][5][6][7][8][9][10][11] for small phosphines and phosphites effect and trans influence are dictated mainly by electronic effects.…”