116198-00-6Relevant articles and documents
Synthesis and characterization of mixed ruthenium/platinum μ4-phosphinidene, phosphorus monoxide, and related clusters
Scoles,Yamamoto,Brissieux,Sterenberg,Udachin,Carty
, p. 6731 - 6736 (2001)
The mixed-metal cluster complexes [Ru4(CO)12Pt(CO)PPh3(μ4-PR)] [R = NiPr2(1), F(3)] were formed by capping the Ru3P face of the nido clusters [Ru4(CO)13(μs
Ruthenium carbonyl cluster complexes with nitrogen ligands. III. Reaction of Ru3(μ-AuPPh3)(μ-Cl)(CO)10 with pyridine; crystal structures of Ru3(μ-H)(μ-NC5H4)(CO)9(PPh3), Ru3(μ-Cl)2(CO)8(NC5H5)(PPh3) and Ru3(μ-Cl)2(CO)8(NC5H5)2
Cifuentes, Marie P.,Humphrey, Mark G.,Skelton, Brian W.,White, Allan H.
, p. 211 - 220 (1994)
The reaction between Ru3(μ-AuPPh3)(μ-Cl)(CO)10 (1) and pyridine afforded a mixture of products from which the title complexes Ru3(μ-H)(μ-NC5H4)(CO)9(PPh3) (4), Ru3(μ-Cl)2(CO)8(NC5H5)(PPh3) (6) and Ru3(μ-Cl)2(CO)8(NC5H5)2 (7) have been obtained together with the previously reported pyridyl cluster Ru3(μ-H)(μ-NC5H4)(CO)10 (2) and the phosphine-substituted clusters Ru3(CO)10(PPh3)2 (3) and Ru3(μ-Cl)2(CO)8(PPh3)2 (5).Complex 4 has also been obtained with a high yield by phosphine substitution of 2 under mild conditions.The structural study of 4 reveals site-specific substitution at the N-ligated ruthenium.Products 5-7 are dichloro-bridged complexes related by successive replacement of PPh3 by NC5H5.Single-crystal X-ray diffraction studies of 6 and 7 indicate that these complexes contain triruthenium cores incorporating one and two ?-bound equatorially disposed pyridine ligands respectively, a new coordination mode for unsupported pyridine ligands on triruthenium clusters.Extremely long Ru-N distances in 6 and 7 are consistent with the lightly stabilizing nature of the pyridine ligand in trinuclear cluster chemistry.A comparison of the core geometries of 5-7 has revealed a contraction in the Ru-Ru distances on sequential replacement of the P-donor ligand by the N-donor ligand. Key words: Ruthenium; Carbonyl; Pyridine; Crystal structure
Oxygen atom transfer to metal carbonyls. Kinetics and mechanism of CO substitution reactions of M3(CO)11L (M = Fe, Ru, Os) in the presence of (CH3)3NO
Shen, Jian-Kun,Gao, Yi-Ci,Shi, Qi-Zhen,Basolo, Fred
, p. 4236 - 4239 (2008/10/08)
The rates and activation parameters are reported for CO-substitution reactions of M3(CO)11L (M = Fe, L = P(OEt)3, P(OMe)3; M = Ru, Os, L = P(OEt)3, P(OMe)3, P(n-Bu)3, PPh3, AsPh3, SbPh3) in the presence of (CH3)3NO. The rates of reaction are second order, first order in (CH3)3NO concentration, first order in M3(CO)11L concentration, and zero order in entering ligand concentration. For phosphite derivatives, the relative rates are M3(CO)11P(OMe)3 > M3(CO)11P(OEt)3. For other ligand-substituted complexes, the rates of reaction increase with increasing stretching frequency of the CO bands in the IR spectra. The mechanism involved appears to be similar to that proposed earlier of attack by the O atom of (CH3)3NO on a C atom of a CO coordinated to an unsubstituted metal atom. The unexpected slow rates for the reactions of M3(CO)11P(OR)3 are discussed in terms of shorter M-M bond distances in the cluster.
