Bio-catalysts and catalysts based on ruthenium(II) polypyridyl complexes imparting diphenyl-(2-pyridyl)-phosphine as a co-ligand (original) (raw)
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Journal of Organometallic Chemistry, 2009
Ruthenium complexes [(g 5-C 5 H 5)Ru(j 1-P-PPh 2 Py)(PPh 3)Cl] (1) and [(g 5-C 5 H 5)Ru(j 2-P-N-PPh 2 Py)(PPh 3)] + (1a) containing diphenyl-2-pyridylphosphine (PPh 2 Py) are reported. Coordinated PPh 2 Py in the complex [(g 5-C 5 H 5)Ru(j 1-P-PPh 2 Py)(PPh 3)Cl] (1) exhibits monodentate behavior. In presence of NH 4 PF 6 in methanol at room temperature it afforded chelated complex [(g 5-C 5 H 5)Ru(j 2-P,N-PPh 2 Py)(PPh 3)] + (1a). Further, 1 reacted with various species viz., CH 3 CN, NaCN, NH 4 SCN and NaN 3 to afford cationic and neutral complexes [(g 5-C 5 H 5)Ru(j 1-P-PPh 2 Py)(PPh 3)L] + and [(g 5-C 5 H 5)Ru(j 1-P-PPh 2 Py)(PPh 3)L] [L = CH 3 CN (1b); CN À (1c); N 3 À (1d) and SCN À (1e)] and it's reaction with N,N-donor chelating ligands dimethylglyoxime (H 2 dmg) and 1,2-phenylenediamine (pda) gave cationic complexes [(g 5-C 5 H 5)Ru (j 1-P-PPh 2 Py)(j 2-N-N)]PF 6 [j 2-N-N = dmg (1f) and pda (1g)]. The complexes 1-1g have been characterized by physicochemical techniques and crystal structures of 1, 1a, 1c, 1e and 1f have been determined by single crystal X-ray analyses. Catalytic potential of the complex 1 has been evaluated in water under aerobic conditions. It was observed that the complex 1 selectively catalyzes reduction of aldehyde into alcohol.
Half-Sandwich Ruthenium-Phosphine Complexes with Pentadienyl and Oxo- and Azapentadienyl Ligands
Organometallics, 2012
The complexes [CpRuCl(PEt 3) 2 ] (1) and [CpRuCl(PMe i Pr 2)(PPh 3)] (2) react with H 2 S in EtOH in the presence of NaBPh 4 furnishing the green persulfide derivatives [{CpRu(L)} 2-(µ-S 2)][BPh 4 ] 2 (L) (PEt 3) 2 , (PMe i Pr 2)(PPh 3)), which were also obtained by reaction of 1 or 2 with elemental sulfur and NaBPh 4 in MeOH. At variance with this, the reaction of [Cp*RuCl-(PEt 3) 2 ] (3) with H 2 S in EtOH afforded the Ru IV hydrido-metallothiol [Cp*RuH(SH)(PEt 3) 2 ]-[BPh 4 ], which has been structurally characterized, derived from the oxidative addition of SH 2 to the electron-rich Ru II moiety {[Cp*Ru(PEt 3) 2 ] + }. This compound is oxidized to yield the persulfide complex [{Cp*Ru(PEt 3) 2 } 2 (µ-S 2)][BPh 4 ] 2 , which was also obtained by reaction of 3 with elemental sulfur. The reaction of 1, 2, and 3 with 2-mercapto-pyridine (HSPy) in EtOH yielded cationic complexes in which HSPy is tautomerized to its 1H-pyridine-thione form as inferred from spectral data. Compound 1 reacts with potassium alkyl-xanthates KS 2 COR (R) Me, Et, i Pr) yielding compounds of the type [CpRu(η 1-S 2 COR)(PEt 3) 2 ], whereas the reaction of 2 and 3 led respectively to the complexes [CpRu(η 2-S 2 COR)(PMe i Pr 2)] and [Cp*Ru(η 2-S 2 COR)(PEt 3)], which contain one bidentate xanthate and one phosphine. The X-ray crystal structure of [Cp*Ru(S 2 CO i Pr)(PEt 3)] was determined. In analogous fashion, the reaction of 1 with sodium diethyldithiocarbamate yielded [CpRu(η 1-S 2 CNEt 2)(PEt 3) 2 ], whereas 2 and 3 afforded the corresponding derivatives [CpRu(η 2-S 2 CNEt 2)(PMe i Pr 2)] and [Cp*Ru(η 2-S 2 CNEt 2)(PEt 3)].