Triphenylphosphine Complexes Of Ruthenium Research Articles

Electronically exited states in triphenylphosphine complexes of Ruthenium (II): TD DFT study

Singlet and triplet electronically exited states (EES) of the luminescent and photoactive complexes [Ru(bpy)2(PPh3) (L)]+2, where bpy is 2,2′- bipyridyl, L is 4-aminopyridine, pyridine (py), or 4,4′- bipyridyl (bipy) are studied within TDDFT/B3LYP/[6‐31G(d)+LanL2DZ(Ru)] method in the energy region of 2.2eV − 4.5eV. We revealed the nature of more than 70 EES and constructed a series of multi-level schemes of the EE states, taking into account 3dd levels of Ru (II) and metal-to-ligand charge-transfer states of pyridine ligands (MLCT(L)). These schemes gave us the opportunity to evaluate the activation energy of 3dd-states of Ru (II) ion and to explain the weak luminescence of triphenylphosphine complexes of Ruthenium (II) (TPRC) at room temperature. Besides, we discovered that the emission energy (Eem) of the principal luminescent transition 3MLCT→1GS of the complexes studied depends linearly on the effective charge on the nitrogen atom (Q(N4)) of the coordinated pyridyl ligand. The electronic absorption spectra of TPRC are calculated and interpreted within TD DFT, and the energy of luminescent transition (ET-S) from the lowest triplet 3MLCT to the ground state for all TPRC under study is evaluated. It is shown that the variation of pyridine ligands (L) from electron donors to electron acceptors results in the hypsochromic shift of ET-S, which is in good agreement with the experimental data.

Rate and selectivity of reduction of alkylcyclohexanones with 2-propanol in presence of triphenylphosphine complexes of ruthenium, rhodium, and iridium

1. The rate and selectivity of the reduction of the 2-, 3-, and 4-alkylcyclohexanones with 2-propanol in the presence of Ru, Rh, and Ir complexes depends on the nature of the central atom, the coupling of the ligands (PPh3, Cl−, CO, OH−, NO−, Me2SO), and the position of the alkyl substituent. A substituent in the 2 position lowers the rate of hydrogen transfer. 2. The complexes RhCl(PPh3)3 and Rh(NO)Cl2(PPh3)2 catalyze the reduction of the 3- and 4-alkylcyclohexanones with 2-propanol to give predominantly the thermodynamically less stable alkylcyclohexanol, while RuCl2(PPh3)3, HRu(CO)Cl(PPh3)3, Ir(CO)(PPh3)2, Rh(CO)Cl(PPh3)2, Rh(Me2SO)Cl(PPh3)2, and Rh(OH) (CO)(PPh3)2 direct the process toward the formation of the thermodynamically more stable alkylcyclohexanol. 3. The reduction of the 2-alkylcyclohexanones in the presence of the investigated complexes of Ru, Ir, and also Rh, devoid of the CO group, proceeds with the predominant formation of the thermodynamically less stable cis-2-alkylcyclohexanol.

Solution behavior of triphenylphosphine complexes of ruthenium(II)

ADVERTISEMENT RETURN TO ISSUEPREVArticleNEXTSolution behavior of triphenylphosphine complexes of ruthenium(II)K. G. CaultonCite this: J. Am. Chem. Soc. 1974, 96, 9, 3005–3006Publication Date (Print):May 1, 1974Publication History Published online1 May 2002Published inissue 1 May 1974https://doi.org/10.1021/ja00816a063RIGHTS & PERMISSIONSArticle Views336Altmetric-Citations31LEARN ABOUT THESE METRICSArticle Views are the COUNTER-compliant sum of full text article downloads since November 2008 (both PDF and HTML) across all institutions and individuals. These metrics are regularly updated to reflect usage leading up to the last few days.Citations are the number of other articles citing this article, calculated by Crossref and updated daily. Find more information about Crossref citation counts.The Altmetric Attention Score is a quantitative measure of the attention that a research article has received online. Clicking on the donut icon will load a page at altmetric.com with additional details about the score and the social media presence for the given article. Find more information on the Altmetric Attention Score and how the score is calculated. Share Add toView InAdd Full Text with ReferenceAdd Description ExportRISCitationCitation and abstractCitation and referencesMore Options Share onFacebookTwitterWechatLinked InReddit PDF (267 KB) Get e-Alerts Get e-Alerts

Reduction of ketones with secondary alcohols, catalyzed by triphenylphosphine complexes of ruthenium and rhodium

1. The reduction rate of cyclohexanone with alcohols in the presence of RuCl2(PPh3)3 is independent of the length of the alkyl of the 2-n-alkanol (C4-C11), or of the presence of either the sec-butyl or cyclohexyl radical, but decreases sharply when going to the 3-,4-,and 5-alkanols and 3,3-dimethyl-2-butanol. The alkylphenylcartainols reduce ketones at a much faster rate than do the 2-alkanols, and they also promote the transformation of the latter. 2. The reduction rate of ketones by alcohols, catalyzed by RuCl2(PPh3)3, decreases in the order; cyclohexanone > acetophenone > cyclopentanone > 2-hexanone ≥ cycloheptanone > cyclooctanone. 3. The catalytic activity of RhCl(PPh3)3 in the hydrogen transfer reaction is higher than that of RuCl2(PPh3)3, and the reaction rate is but slightly dependent on the structures of the alcohol and the ketone.

Complexes of the platinum metals. Part II. Carboxylato(triphenylphosphine) derivatives of ruthenium, osmium, rhodium, and iridium

Many hydrido- and low oxidation state triphenylphosphine complexes of ruthenium, osmium, rhodium, and iridium are shown to yield carboxylato-derivatives on reaction with carboxylic acids R·CO2H (R = alkyl or aryl) in organic solvents. These reactions provide convenient syntheses for an extensive range of new and previously reported series of carboxylato-complexes including RuH(OCOR)(PPh3)3, RuCl(OCOR)(CO)(PPh3)2, RuH(OCOR)(CO)(PPh3)2 Ru(OCOR)2(CO)(PPh3)2, Ru(OCOR)2(CO)2(PPh3)2, OsH(OCOR)(PPh3)3, Rh(OCOR)(PPh3)3, Rh(OCOR)(CO)(PPh3)2[Rh(Ph2P·CH2·CH2·PPh2)2][OCOR], Rh(OCOR)2(NO)(PPh3)2, IrH2(OCOR)(PPh3)3, and Ir(OCOR)3(PPh3)2. A single-step synthesis of the complexes RuH(OCOR)(PPh3)3 from hydrated ruthenium trichloride is also described. The carboxylato-derivatives are characterised by i.r. and 1H n.m.r. spectroscopy.

Triphenylphosphine complexes of ruthenium and rhodium. Reversible combinations of molecular nitrogen and hydrogen with the ruthenium complex

Triphenylphosphine complexes of ruthenium and rhodium. Reversible combinations of molecular nitrogen and hydrogen with the ruthenium complex