77611-27-9Relevant academic research and scientific papers
Catalytic studies with ruthenium clusters substituted with diphosphines. Part II. Studies with Ru3(CO)8(Ph2PCH2PPh2)2
Fontal,Reyes,Suarez,Bellandi,Ruiz
, p. 87 - 97 (1999)
The catalytic reactions of Ru3(CO)8(dppm)2 (dppm = Ph2PCH2PPh2) under hydrogen pressure were investigated. The Ru3(CO)10(dppm) complex showed activity with 1-hexene favoring isomerixation to cis-2-hexene at lower hydrogen pressures and complete hydrogenation at higher temperature and pressure. The reaction was first order on substrate with a keff = 1.59 x 10-3/min. Turnover studies implied cluster analysis. The catalytic activity was demonstrated for other unsaturated organic substrates.
Triruthenium clusters containing bridging dppm and capping sulfido and selenido ligands: (see abstract)
Kabir, Shariff E.,Ahmed, Syed J.,Hyder, Md. Iqbal,Miah, Md. Arzu,Bennett, Dennis W.,Haworth, Daniel T.,Siddiquee, Tasneem A.,Rosenberg, Edward
, p. 3412 - 3420 (2004)
The reaction of [Ru3(CO)10(μ-dppm)] (1) with dppmSe at 66 °C affords [Ru3(CO)8(μ-dppm) 2] (2), [Ru3(CO)7(μ3-CO) (μ3-Se)(μ-dppm)] (3), [Ru3(CO)5 (μ3-CO)(μ3-Se)(μ-dppm)2] (4) and [Ru3(CO)6(μ3-CO)(μ3 -Se)(μ-dppm)(η1-Ph2PCH2P(=O) Ph2)] (5) in 7%, 5%, 9% and 33% yields, respectively. A similar reaction between 1 with dppmS gives [Ru3 (CO)7(μ3-S)2(μ-dppm)] (6), [Ru3(CO)7(μ3-CO)(7μ3-S) (μ-dppm)] (7) [Ru3(CO)5(μ3-CO) (μ3-S)(μ-dppm)2] (8) and [Ru3 (CO)6(μ3-CO)(μ3-S)(μ-dppm) (η1-Ph2PCH2P(=O)Ph2)] (9) in 8%, 7%, 14% and 35% yields, respectively. Treatment of 1 with PhSeSePh at 66 °C affords the dinuclear compound [Ru2(CO) 4(μ-SePh)2(μ-dppm)] (10) in 14% yield. Thermolysis of 5 and 9 in refluxing toluene at 110 °C gives 4 and 8, respectively. The molecular structures of 4, 9 and 10 have been determined by single-crystal X-ray diffraction studies. The cores of the new clusters 4, 5, 8 and 9 consist of metal triangles capped by μ3-sulfur or selenium atoms with the bidentate ligand bridging in equatorial positions. In compounds 4 and 8, two bidentate dppm ligands bridge the Ru3 triangle in such a way that each ligand bridges two ruthenium atoms and one Ru-Ru edge remains unbridged. Compounds 5 and 9 contain one bridging dppm ligand and one dangling dppm mono-oxide ligand Ph2PCH2P(=O)Ph2 coordinated to the rear metal atom at an equatorial position. The molecular structure of 10 shows classical sawhorse structure with two bridging SePh ligands as well as the dppm ligand.
Kinetics of reaction of bis(diphenylphosphino)methane with dodecacarbonyltriruthenium
Ambwani, Bimla,Chawla, Sudhir,Po?, Anthony
, p. 2635 - 2638 (2008/10/08)
Reaction of dppm (Ph2PCH2PPh2) with Ru3(CO)12 proceeds via the complexes Ru3(CO)10(μ-dppm) and Ru3(CO)9(μ-dppm)(η1-dppm) to form the very stable Ru3(CO)8(μ-dppm)2, and the kinetics of the three reactions in benzene have been followed. Reaction with Ru3(CO)12 proceeds mainly by a ligand-dependent path, and dppm is about twice as nucleophilic as PPh3 toward this cluster. Ru3(CO)10(μ-dppm) reacts with dppm to form Ru3(CO)9(μ-dppm)(η1-dppm) by two paths. The main path (ca. 80%) follows kinetics characteristic of a reversible CO dissociative path. The minor path is completely inhibited by CO, even at high [dppm], and may involve dissociation of CO from an already substituted Ru atom before transfer of the unsaturation to the Ru(CO)4 moiety. The bridge formation reaction undergone by Ru3(CO)9(μ-dppm)(η1-dppm) to give the final product also occurs via two paths, but in this case they are of approximately equal importance. One is not affected by CO and is assigned to dissociative loss of CO from a bridged Ru atom, formation of the second bridge following very rapidly. The other may involve reversible loss of CO from the Ru(CO)3(η1-dppm) moiety followed by transfer of the unsaturation to one of the other Ru atoms.
Lewis acid bonding to triruthenium and triosmium clusters. The crystal and molecular structure of Ru3(μ-Ph2PCH2PPh2) 2(CO)8(μ-AgO2CCF 3)?1/2CH2Cl2 and spectroscopic studies of related adducts
Ladd, Judith A.,Hope, Hakon,Balch, Alan L.
, p. 1838 - 1846 (2008/10/08)
Ru3(μ-dpm)2(CO)8 (dpm is bis(diphenylphosphino)methane) forms weakly bound adducts Ru3(μ-dpm)2(CO)8?(μ-A) (A = AgO2CCF3, Hg(O2CCF3)2, Cu(NCCH3)BF4, HO2CCF3) that have been characterized by electronic, infrared, and 31P NMR spectroscopy. Equilibrium constants for adduct formation increase in the order H+ + 2+ +. Ru3(μ-dpm)2(CO)8(μ-AgO 2CCF3)·1/2CH2Cl2 crystallizes in the orthorhombic space group Pca21 (No. 29) with four molecules per unit cell of dimensions a = 20.706 (9) A?, b = 15.693 (11) A?, and c = 18.447 (5) A? at 140 K. The structural study shows that the AgO2CCF3 unit binds through silver across the exposed edge of the triruthenium cluster. The adduct contains two adjacent, nearly coplanar triangles of the four metal atoms. The addition of Ag+ to the Ru-Ru bond results in an 0.167 A? lengthening of the Ru-Ru separation and some bending of the in-plane carbonyl groups away from the silver binding site. Similar adducts of silver trifluoroacetate with Ru3(CO)12, Os3(CO)12, and some substituted derivations of Ru3(CO)12 have been detected in solution.
CLUSTER CHEMISTRY. XVII. RADICAL ION-INITIATED SYNTHESES OF RUTHENIUM CLUSTER CARBONYLS CONTAINING TERTIARY PHOSPHINES, PHOSPHITES, ARSINES, SbPh3 OR ISOCYANIDES
Bruce, Michael I.,Matisons, Janis G.,Nicholson, Brian K.
, p. 321 - 344 (2007/10/02)
The syntheses of over sixty known and new derivatives of Ru3(CO)12 and H4Ru4(CO)12 by substitution reactions initiated by sodium diphenylketyl are described.The range of ligands studied includes isocyanides, tertiary phosphines and phosphites, tertiary ar
