16369-40-7Relevant academic research and scientific papers
A Hybrid Ru(II)/TiO2Catalyst for Steadfast Photocatalytic CO2to CO/Formate Conversion following a Molecular Catalytic Route
Back, Changhyun,Choe, Min Su,Choi, Sunghan,Kang, Sang Ook,Kim, Chul Hoon,Kim, So-Yoen,Lee, Daehan,Lee, Hyun Seok,Son, Ho-Jin
, p. 10235 - 10248 (2021)
Herein, we employed a molecular Ru(II) catalyst immobilized onto TiO2 particulates of (4,4′-Y2-bpy)RuII(CO)2Cl2 (RuP; Y = CH2PO(OH)2), as a hybrid catalyst system to secure the efficient and steady catalytic activity of a molecular bipyridyl Ru(II)-complex-based photocatalytic system for CO2 reduction. From a series of operando FTIR spectrochemical analyses, it was found that the TiO2-fixed molecular Ru(II) complex leads to efficient stabilization of the key monomeric intermediate, RuII-hydride (LRuII(H)(CO)2Cl), and suppresses the formation of polymeric Ru(II) complex (-(L(CO)2Ru-Ru(CO)2L)n-), which is a major deactivation product produced during photoreaction via the Ru-Ru dimeric route. Active promotion of the monomeric catalytic route in a hetero-binary system (IrPS + TiO2/RuP) that uses TiO2-bound Ru(II) complex as reduction catalyst led to highly increased activity as well as durability of photocatalytic behavior with respect to the homogeneous catalysis of free Ru(II) catalyst (IrPS + Ru(II) catalyst). This catalytic strategy produced maximal turnover numbers (TONs) of >4816 and >2228, respectively, for CO and HCOO- production in CO2-saturated N,N-dimethylformamide (DMF)/TEOA (16.7 vol % TEOA) solution containing a 0.1 M sacrificial electron donor.
Surface-mediated organometallic synthesis: High-yield preparations of {Ir(CO)3Cl}n, [Rh(CO)2Cl]2, [Ru(CO)3Cl2]2, [Os(CO)3Cl2]2, [Ir4(CO)12], and [Rh6(CO)16] by reductive carbonylation, under mild conditions, of silica-supported metal chlorides
Roberto, Dominique,Psaro, Rinaldo,Ugo, Renato
, p. 2292 - 2296 (2008/10/08)
{Ir(CO)3Cl}n, [Rh(CO)2Cl]2, [Ru(CO)3Cl2]2, and [Os(CO)3Cl2]2 have been synthesized in high yield from the corresponding metal trichloride supported on a silica surface by reductive carbonylation at atmospheric pressure. With IrCl3·nH2O, the synthesis can be directed to give selectively [Ir4(CO)12] by working at 70°C in the presence of CO and H2O. [Rh6(CO)16] has also been prepared by reductive carbonylation at room temperature of silica-supported [Rh(CO)2Cl]2. These surface-mediated synthetic methods give yields comparable or often higher than those of the traditional solution syntheses.
Synthesis and characterization of transition metal complexes of (2-(2-methoxyethoxy)ethyl)diphenylphosphine and (2-(2-methoxyethoxy)ethyl)dimethylarsine
Reddy, V. Vijay Sen,Whitten, J. E.,Redmill, K. A.,Varshney, A.,Gray, G. M.
, p. 207 - 216 (2007/10/02)
Two new, potentially tridentate ligands, Ph2P(CH2CH2O)2Me (POO) and Me2As(CH2CH2O)2Me (AsOO), have been synthesized and characterized by multinuclear NMR spectroscopy.Mononuclear complexes of these ligands, cis-(CO)4Mo(EOO)2 (E = P, As) cis,cis,trans- and cis,trans,cis-(CO)2Cl2Ru(POO)2, and Cl2M(POO)2, (M = Pd and Pt), have also been prepared and characterized by multinuclear NMR and IR spectroscopy.In all cases, these ligands are coordinated only through the group 15 donor atom.Different procedures have been developed to give either the cis,cis,trans or cis,trans,cis isomers of Cl2(CO)2Ru(POO)2 complex in high yields.The latter isomer is unusual and has not previously been reported with ligands of this type.The reactions of the cis-(CO)4Mo(EOO)2 complexes with methyllithium have been examined.The carbonyl ligands in these complexes do not react with methyllithium at room temperature.These results are in direct contrast to those of Powell and coworkers who reported facile reactions between methyllithium and the carbonyl ligands in similar cis-(CO)4Mo(Ph2PO(CH2CH2O)3PPh2) complexes.These results confirm Powell's conclusions that the number and type of the hard donor atoms in these complexes greatly affect the reactivity of methyllithium towards the carbonyl ligands.
Metal complexes containing diastereoisomers and enantiomers of o-phenylenebis(methylphenylarsine) and its Phosphorus analogue. 4. Preparation and properties of carbonyl halide derivatives of ruthenium(II)
Grocott, Stephen C.,Wild, Stanley Bruce
, p. 3535 - 3540 (2008/10/08)
Octahedral complexes of the type [RuCl2(CO)2(bidentate)] have been prepared from the meso, racemic, and optically active forms of o-phenylenebis(methylphenylarsine) and its phosphorus analogue. Methods are described for the production of either the cis- or trans-dichloro isomers. The salts [RuCl(CO)3(bidentate)]Cl were also isolated in the case of the di(tertiary phosphines) and shown to contain a meridional arrangement of carbonyl ligands. The neutral dicarbonyls underwent reversible decarbonylation to form the chloro-bridged dimers [RuCl2(CO)(bidentate)]2. Reaction of the dimers or neutral dicarbonyls with dimethyl sulfoxide gave exclusively the cis-dichloro complexes [RuCl2(CO)(bidentate)(Me2SO-S)]. The latter were shown to undergo a slow epimerization at the metal center which was facilitated by heating, according to variable-temperature 1H NMR studies. The structures of the various stereoisomeric complexes were assigned on the basis of spectroscopic data and, in two instances, X-ray crystallography.
