114674-45-2Relevant academic research and scientific papers
Correlations among 31P NMR Coordination Chemical Shifts, Ru-P Bond Distances, and Enthalpies of Reaction in Cp′Ru(PR3)2Cl Complexes (Cp′ = η5-C5H5, η5-C5Me5
Hunter, Alex D.,Williams, Trevor Robert,Zarzyczny, Brandon M.,Bottesch, Hans W.,Dolan, Sara A.,McDowell, Kimberly A.,Thomas, Dominique Nicole,Mahler, Charles H.
, p. 2701 - 2706 (2016/09/04)
The 31P NMR spectra of CpRu(PR3)2Cl and Cp?Ru(PR3)2Cl complexes with PR3 = PMe3, PPhMe2, PPh2Me, PPh3, PEt3, PnBu3/su
Oxidative reactions of half-sandwich ruthenium compounds: Formation of cationic nitrosyl ruthenium(II) derivatives
Diversi, Pietro,Fontani, Marco,Fuligni, Melania,Laschi, Franco,Matteoni, Simona,Pinzino, Calogero,Zanello, Piero
, p. 145 - 156 (2007/10/03)
The electrochemical behaviour of the ruthenium(II) alkyl complexes [Ru(Me)Cp*(L)2] (Cp=η5-C5Me5; L=PMe3 2a, PMe2Ph 2b), [Ru(CH2CMe3)Cp*(PMe3)2] (3a), and the related [Ru(Me)Cp(PPh3)2] (4d) (Cp=η5-C5H5) in CH2Cl2 involves a one-electron process, yielding the corresponding ruthenium(III) paramagnetic cations, as shown by coupled electrochemical-EPR studies. Compounds 2-4 are oxidised by [FeCp2]+ in benzene to unidentified paramagnetic products which may decompose giving the corresponding alkane. The Cp* compounds react with NOBF4 affording the monocationic alkylnitrosyl derivatives [Ru(R)Cp*(NO)(L)]BF4 (R=Me; L=PMe3 7a, PMe2Ph 7b. R=CH2CMe3; L=PMe3) and, when in excess of NO+, the ruthenium(II) dicationic complexes [RuCp*(NO)(L)2](BF4)2 (L=PMe3 5a, PMe2Ph 5b). The chloro complexes [Ru(Cl)Cp*(L)2] (L=PMe3 1a, PMe2Ph 1b, PPh3 1d) react analogously with NO+ to give [Ru(Cl)Cp*(NO)(L)]BF4 (L=PMe3 6a, PMe2Ph 6b, PPh3 6d) and [RuCp*(NO)(L)2](BF4)2 (L=PMe3 5a, PMe2Ph 5b). In contrast [Ru(Me)Cp(PPh3)2] gives only [Ru(Me)Cp(NO)(PPh3)]BF4. EPR spectroscopy suggests that these nitrosylation reactions are also oxidative in character proceeding through ruthenium(III) intermediates.
Correlation between Structural and Solution Calorimetric Data for Cp*Ru(PR3)2Cl (Cp* = C5Me5) Complexes
Smith Jr., Dale C.,Haar, Christopher M.,Luo, Lubin,Li, Chunbang,Cucullu, Michèle E.,Mahler, Charles H.,Nolan, Steven P.,Marshall, William J.,Jones, Nancy L.,Fagan, Paul J.
, p. 2357 - 2361 (2008/10/08)
Single-crystal X-ray diffraction studies were conducted on the following compounds: Cp*Ru(PMe3)2Cl (1), Cp*Ru(PPhMe2)2Cl (2), Cp*Ru(PMePh2)2Cl (3), Cp*Ru(PPh3)2Cl (4),
Organoruthenium thermochemistry. Enthalpies of reaction of (Cp*RuCl)4 and Cp*Ru(COD)Cl (Cp* = η5-C5Me5, COD = cyclooctadiene) with dienes and tertiary phosphine ligands
Luo, Lubin,Nolan, Steven P.,Fagan, Paul J.
, p. 4305 - 4311 (2008/10/08)
The enthalpies of reaction of Cp*Ru(COD)Cl(Cp* = η5-C5Me5, COD = cyclooctadiene) with a series of monodentate ligands, leading to the formation of Cp*Ru(ER3)2Cl (E = P, As), have been measured by anaerobic solution calorimetry in THF at 30°C. The enthalpies of reaction associated with the rapid and quantitative reaction of the (Cp*RuCl)4 complex with diene ligands in THF at 30°C, producing Cp*Ru(diene)Cl complexes, have also been investigated. Reaction of (Cp*RuCl)4 with excess phosphine ligand, at 30°C, has been shown to quantitatively yield the corresponding Cp*Ru(PR3)2Cl complex and allows for the design of a thermochemical cycle assuring the internal consistency of the thermochemical data. The overall relative order of stability established for the preceding complexes is as follows: for monodentate ligands, AsEt3 3 nBu3 3 2Me 3 2 3 3; for dienes, 2,3-dimethyl-1,3-butadiene 1,3-cyclohexadiene cyclooctadiene 1,3-pentadiene norboraadiene. Comparisons with other organometallic systems and insight into factors influencing the Ru-L bond disruption enthalpies are discussed.
H-C Bond Cleavage by (ν5-Cyclopentadienyl)bis(triorganylphosphine)ruthenium Organyl Complexes
Lehmkuhl, Herbert,Bellenbaum, Marita,Grundke, Juergen,Mauermann, Heiko,Krueger, Carl
, p. 1719 - 1728 (2007/10/02)
Ruthenium(II) complexes of the type Cp(MenPh3-nP)2RuR with R = CH3, and R = CH2CMe3 have been prepared from the appropriate ruthenium chloride and alkyllithium or alkylmagnesium chloride.Of the methyl complexes having at least one phenyl group in the phosphane ligand, 17 reacts at 20 deg C and 14, 19, and 21 upon warming by intramolecular H-C(phenyl) bond cleavage and elimination of methane to give the ortho-metallated products Cp(MenPh3-nP) 15, 18, 20, and 22.The neopentyl ruthenium complexes 23, 25, 32, 34, and 36 react in an intermolecular manner with benzene by H-C(benzene) bond cleavage and elimination of neopentane to give the phenylruthenium compounds 24, 26, 33, 35, and 37.Whereas the Me3P-complex 36 as well as (C5H5)(Me3P)(Ph3P)RuCH2CMe3 (30) react with benzene to give neopentane and the phenyl complexes 37 and 31, the complexes 23, 25, 32, and 34 react to give undeuterated neopentane and the phenyl compounds 24, 26, 33, and 35.The phenyl complex 24 and the ruthenium compounds having benzyl (34) or p-tolyl groups (40) react with toluene to give an equilibrium mixture of the m- and p-tolyl complexes 38 and 40.H-C(arene) bond cleavage is also observed with other aromatic compounds such as phenyl bromide or naphthalene.In the case of 36 bond cleavage occurs selectively in the position meta to the substituent to give 42 and 43.Styrene, in contrast, reacts with 36 with cleavage of the vinylic 1(E)-H-C bond to give 44, while ethylene reacts to give the (ν2-ethylene)-vinylruthenium complex 45, which upon warming isomerizes with ethylene insertion into the vinyl-Ru bond to give the ν3-1-methylallyl compound 46. - In the H-C bond cleavage reaction, (C5Me5)Ru complexes are more reactive than the corresponding systems with a C5H5 group, and in both series the reactivity decreases with increasing basicity of the phosphine ligand. - The crystal structure analysis of Cp(Ph3P)(Me3P)RuCH2CMe=CH2 (13) is described.
