16592-00-0

Basic information

• Product Name: Ru(CO)3(P(c-Hex)3)2
• Synonyms: Ru(CO)3(P(c-Hex)3)2
• CAS NO: 16592-00-0
• Molecular Weight: 745.969
• Mol File: 16592-00-0.mol

Chemical Properties

• CAS DataBase Reference: Ru(CO)3(P(c-Hex)3)2(CAS DataBase Reference)
• NIST Chemistry Reference: Ru(CO)3(P(c-Hex)3)2(16592-00-0)
• EPA Substance Registry System: Ru(CO)3(P(c-Hex)3)2(16592-00-0)

Safety Data

• Hazardous Substances Data: 16592-00-0(Hazardous Substances Data)

Upstream product

• 16594-66-4 {RuI(CO)3((C₆H₁₁)3P)2}⁽¹⁺⁾*{AlICl₃}^(1-)={RuI(CO)3(C₁₈H₃₃P)2}{AlICl₃} 
• 182682-80-0 Ru(CO)2(P(C₆H₁₁)3)2 
• 201230-82-2 carbon monoxide 
• 187793-39-1 [RuH2[(η(2)-HSiMe2)2(C6H4)](PCy3)2] 
• 121808-99-9 ax-Ru(CO)4(P(cy)3) 
• 2622-14-2 tricyclohexylphosphine 
• 14898-67-0 ruthenium trichloride hydrate 
• 124592-67-2 Ru(CO)2(bis(2,6-diisopropylmethyl)-1,4-diaza-1,3-butadiene)(P(c-Hex)3) 

Downstream Products

• 77520-51-5 [(P(C₆H₁₁)3)2Ru(carbonyl)2(hydrido)2] 
• 158250-38-5 cic,cis,trans-[Ru(CO)2(H)2(tricyclohexylphosphine)2] 
• 135972-74-6 {Ru(P(C₆H₁₁)3)2(CO)3}⁽¹⁺⁾*PF₆^(1-)={Ru(P(C₆H₁₁)3)2(CO)3}{PF₆} 
• 29079-65-0 Ru(CO)2Br₂(P(C₆H₁₁)3)2 

Relevant articles and documents

Ligand (L) influence on CO binding enthalpies to Ru(CO)2L2

Reaction enthalpies for the addition of CO to Ru(CO)2L2 (L = PtBu2Me, PiPr3, and PCy3) in toluene are -26.2(3), -31.4(2), and -28.9(4) kcal/mol, respectively. These are larger than the enthalpies of reaction with MeNC, PhC≡CPh, and PhCC-H. PtBu2Me consistently gives the least amount of enthalpy released, but only when CO (and MeNC) is the reagent does PiPr3 yield a more exothermic enthalpy of reaction than PCy3. The generally subtle influences on ΔH by PiPr3 and PCy3 are rationalized in terms of the contradictory steric and electronic effects as isopropyl is replaced by cyclohexyl.

Ruthenium complexes containing two Ru-(η2-Si-H) bonds: Synthesis, spectroscopic properties, structural data, theoretical calculations, and reactivity studies

The bis(dihydrogen) complex RuH2(H2)2(PCy3)2 (1) reacts with the disilanes (R2SiH)2X to produce the dihydride complexes [RuH2{(η2-HSiR2)2X}(PCy 3)2] (with R = Me and X = O (2a), C6H4 (3), (CH2)2 (4), (CH2)3 (5), OSiMe2O (6)) and R = Ph, X = O (2b)). In these complexes, the bis(silane) ligand is coordinated to ruthenium via two σ-Si-H bonds, as shown by NMR, IR, and X-ray data and by theoretical calculations. 3, 4, and 6 were characterized by X-ray diffraction. In the free disilanes the Si-H bond distances and the JSi-H values are around 1.49 A and 200 Hz, respectively, whereas in the new complexes the values are in the range 1.73-1.98 A and 22-82 Hz, respectively for the σ-Si-H bonds. The importance of nonbonding H...Si interactions, which control the observed cis geometry of the two bulky PCy3 ligands, is highlighted by X-ray data and theoretical calculations. The series of bis(silane) model complexes, RuH2{(η2-HSiR2) 2X}(PR′3)2, with X = (CH)2, C6H4, (CH2)n, O, and OSiH2O, and with R and R′ = H or Me, was investigated by density functional theory (DFT) by means of two hybrid functional B3LYP and B3PW91. In the case of X = C6H4 three isomers were studied, the most stable of which has C2v symmetry and whose structure closely resembles the X-ray structure of 3. Calculated binding energies for the bis(silane) ligand to the RuH2(PH3)2 fragment vary from 130 to 192 kJ/mol, showing that in the more stable complexes, the Si-H bonds are bound more strongly than dihydrogen. The dynamic behavior of these complexes has been studied by variable temperature 1H and 31P{1H} NMR spectroscopy and exchange between the two types of hydrogen is characterized by barriers of 47.5 to 68.4 kJ/mol. The effect of the bridging group X between the 2 silicons is illustrated by reactions of compounds 2-6 with H2, CO, tBuNC. 3 is by far the most stable complex as no reaction occurred even in the presence of CO, whereas elimination of the corresponding disilane and formation of RuH2(H2)2-(PCy3)2, RuH2(CO)2(PCy3)2, or RuH2(tBuNC)2(PCy3)2 were observed in the case of 2 and 4-6. The mixed phosphine complexes [RuH2{(η2-HSiMe2)2X}(PCy 3)(PR3)] 3R-6R (with R = Ph and R = pyl) have been isolated in good yields (80-85%) and fully characterized by the addition of 1 equiv of the desired phosphine to 3-6. In the case of 4Ph, an X-ray determination was obtained. In the case of 2, elimination of the disiloxane was always observed. Addition of 1 equiv of a disilane to Ru(COD)(COT) in the presence of 2 equiv of the desired phosphine under an H2 atmosphere produces the complexes [RuH2{(η2-HSiMe2)2X}(PR 3)2] (X = C6H4, R = Ph (3Ph2) and R = pyl (3pyl2); X = (CH2)2, R = Ph, 4Ph2; R = pyl, 4pyl2). 4Ph2 was also characterized by an X-ray structure determination.

Mechanism of halide-induced disproportionation of M(CO)3(PCy3)2+ 17-electron radicals (M = Fe, Ru, Os). Periodic trends on reactivity and the role of ion Pairs

Halide-induced disproportionation of the 17-electron M(CO)3(PCy3)2+ radicals was probed by double potential step chronocoulometry, rotating-ring-disk electrochemistry, bulk coulometry, and cyclic voltammetry. Th

Systematic substituent effects on dissociative substitution kinetics of Ru(CO)4L complexes (L = P-, As-, and Sb-donor ligands)

The kinetics of dissociation of CO from Ru(CO)4L (L = a wide variety of P-, As-, and Sb-donor ligands) have been studied, and the values of the rate constants can be resolved quantitatively into electronic and steric effects. The curved steric profile obtained shows that steric effects are quite small for small substituents such as P(OCH2)3CEt and P(OEt)3, but they increase steadily and substantially as the size of the substituent increases. A similar analysis of data in the literature for CO dissociative reactions of other substituted carbonyl complexes is also successful in resolving electronic and steric effects, and a clear dependence of steric effects on the coordination number of the complexes is shown. The analysis can be applied to some methyl migration reactions that involve CO loss, and the results can help to indicate the relative importance of CO loss and methyl migration in the transition states. Trends in the C-O stretching frequencies in the axial Ru(CO)4L and diaxial Ru(CO)3L2 complexes are described.

The influence of substitution of CO by PR3 on the photochemistry of Fe(CO)3(i-Pr2Ph-DAB) and Ru(CO)3(i-Pr2CH-DAB) (DAB=1,4-diaza-1,3-butadiene); a flash-photolysis and low-temperature study

The result are presented of a photochemical study of the complexes Fe(CO)3(i-Pr2Ph-DAB) and Ru(CO)3(i-Pr2CH-DAB) and of some of their PR3-containing derivatives.The reaction were studied by flash-photolysis with 308 nm laser light and by irradiation at various temperatures and exciting wavelengths.Both tricarbonyls show release of CO from the 3LF state but no reaction from 3ML state of the metal R-DAB metallacycle at lower energy.In contrast, Fe(CO)2(i-Pr2Ph-DAB)(P(OPh)3) undergoes breaking of a metal-nitrogen bond from the 3LF state, but this reaction is followed by a fast back-reaction to regenerate the parent compound.As a result on ly a reaction from the 3ML state is observed, in which the i-Pr2Ph-DAB ligand changes its coordination from ?,?-N,N' into η4-CN,C'N'.For the complexes Ru(CO)2(i-Pr2CH-DAB)(PR3) breaking of the metal-nitrogen bond from the 3LF state leads to release of the i-Pr2CH-DAB ligand and formation of Ru(CO)2(PR3)3 and Ru(CO)3(PR3)2.Low-energy irradiation into the ML band gives rise to the formation of Ru(CO)2(η4-i-Pr2CH-DAB)(PR3) from the 3ML state.These differences in photochemical behaviour between the tricarbonyl complexes and their PR3-derivates are discussed in detail.