32613-25-5Relevant academic research and scientific papers
Binding and activation of halocarbons by iron(II) and ruthenium(II)
Kulawiec, Robert J.,Faller,Crabtree, Robert H.
, p. 745 - 755 (1990)
A series of cyclopentadienylruthenium(II) and -iron(II) complexes contain intact iodoalkanes, p-iodotoluene, or chelating (P, X) (o-halophenyl)diphenylphosphine (X = Cl, Br) ligands. The halocarbons coordinate via σ-donation of a halogen lone pair and ret
Efficient transfer of dithiolene ligands from nickel to cyclopentadienyl ruthenium complexes
Adams, Harry,Alasali, Deena M.,Morris, Michael J.,Morris, Sarah A.,Robertson, Craig C.,Robinson, Voirrey L.
, (2019)
The reaction of [CpRu(PPh3)2Cl] with [Ni(S2C2Ph2)2] in refluxing toluene produces the purple salt [CpRu(S2C2Ph2)(PPh3)][Cl], containing a rare ex
Kinetics of substitution of weakly coordinating nitrate by chloride in (η5-Cp)Ru(CO)(ER3)ONO2 (ER3 = AsPh3, PPh3, P(p-anisyl)3, PPh2(o-anisyl), P(OPh)3) in dichloromethane
Cao, Minhton,Do, Liem V.,Hoffman, Norris W.,Kwan, Man-Lung,Little, Julie K.,McGilvray, J. Michael,Morris, Christopher B.,S?derberg, Bjorn C.,Wierzbicki, Andrzej,Cundari, Thomas R.,Lake, Charles H.,Valente, Edward J.
, p. 2270 - 2279 (2008/10/08)
The d6 complexes of formula (η5-Cp)Ru(CO)(ER3)ONO2, where ER3 = AsPh3, PPh3, P(p-anisyl)3, PPh2(o-anisyl), and P(OPh)3, were prepared by reaction of their chloro analogues with AgNO3 in CH2Cl2. They underwent moderately slow substitution of the relatively weakly coordinating nitrate by chloride in dry CH2Cl2 in the presence of excess [N(PPh3)2+]Cl-. A kinetics study showed the reaction to be first order in nitrato complex and independent of chloride salt concentration under pseudo-first-order conditions. First-order rate constants for nitrate metathesis follow the trend P(OPh)3 3 3 3 ? PPh2(o-anisyl), with k1 at 25 °C for the first four in the series from 1.4 to 4.4 × 10-5 s-1. Activation parameters for conversion of (η5-Cp)Ru(CO)(AsPh3)ONO2 to its chloride are ΔH? = 17(2) kcal/mol and ΔS? = -21(5) eu. Even use of a slightly moist solvent increased the rate of nitrate metathesis by 20-30% without changing the form of the rate law. The complex containing PPh2(o-anisyl) was approximately 2 orders of magnitude more reactive (k1 = 4.9 × 10-3 s-1). A likely explanation is stabilization of a coordinatively unsaturated intermediate by weak coordination of the potentially chelating o-OMe group. A mechanism entailing rate-limiting conversion of the neutral nitrato complex into a coordinatively unsaturated ion-paired species is consistent with this set of data. Semiempirical calculations (PM3(tm)), which model the structures of complexes in these systems quite well, supported such behavior. X-ray crystal structures were determined for the AsPh3 nitrato and chloro complexes and for the PPh3 chloro complex.
Ruthenium-catalyzed hydration of 1-alkynes to give aldehydes: Insight into anti-Markovnikov regiochemistry
Tokunaga,Suzuki,Koga,Fukushima,Horiuchi,Wakatsuki
, p. 11917 - 11924 (2007/10/03)
The mechanism of the selective conversion of 1-alkynes to aldehydes by hydration was investigated by isolating organic and organometallic byproducts, deuterium-labeling experiments, and DFT calculations. The D-labeled acetylenic hydrogen of 1-alkyne was found exclusively in the formyl group of the resulting aldehydes. After the reaction, the presence of metal-coordinated CO was confirmed. All of the experimental results strongly suggest the involvement of a metal-acyl intermediate with the original acetylenic hydrogen also bound to the metal center as a hydride, with the next step being release of aldehyde by reductive elimination. Theoretical analyses suggest that the first step of the catalytic cycle is not oxidative addition of acetylene C-H or tautomerization of η2-alkyne to a vinylidene complex, but rather protonation of the coordinated 1-alkyne at the substituted carbon to form a metal-vinyl intermediate. This cationic intermediate then isomerizes to Ru(IV)-hydride-vinylidene via α-hydride migration of the vinyl group to the metal center, followed by attack of the vinylidene α-carbon by OH- to give the metal-hydride-acyl intermediate.
Reduction of a diruthenium bridging vinylidene species Cp2Ru2(μC=CH2) (CO) (μ-CO) (MeCN) by hydrosilane leading to a vinyl complex Cp2Ru2(μ-CH=CH2) (CO)2(SiR3) and vinylsilane: A model system for production of an olefinic product from a vinylidene intermediate
Hua, Ruimao,Akita, Munetaka,Moro-oka, Yoshihiko
, p. 177 - 183 (2008/10/08)
Treatment of the labile diruthenium bridging vinylidene species, Cp2Ru2(μ-C=CH2) (μ-CO) (CO) (MeCN) (7), with hydrosilane produces the silylated bridging vinyl complex, Cp2Ru2(μ-η1:η2-CH=CH 2) (SiR3) (CO)2 (8), from which vinylsilane CH2=CH-SiR3 (19) is eliminated upon further treatment with 2e-donors. The reaction sequence, where hydrosilane works as a pseudohydrogen, can be viewed as a model system for production of an olefinic product from a vinylidene species on a heterogeneous catalyst surface. A similar reaction of 7 with HSnPh3 gives small amounts of ethylene and Cp2Ru2(μ-H)2(SnPh3) 2(CO)2 (20). The molecular structure of the SiMe2Ph derivative of 8 has been determined by X-ray crystallography.
CYCLOPENTADIENYL-RUTHENIUM AND -OSMIUM COMPLEXES V. SYNTHESIS, REACTIVITY AND CRYSTAL STRUCTURE DETERMINATION OF CARBONYLCHLORO(η-CYCLOPENTADIENYL)-(TRIPHENYLPHOSPHINE)RUTHENIUM(II)
Wilczewski. Tadeusz,Dauter, Zbigniew
, p. 349 - 356 (2007/10/02)
CpRuCl(CO)PPh3 is formed as the result of refluxing CpRuCl(PPh3)2 in ethylene glycol (yield up to 15percent).A dissociation process is postulated with liberation of one PPh3 molecule and simultaneous rearrangement of the cation formed earlier: +Cl- -> CpRuCl(CO)PPh3 + PPh3.CpRuCl(CO)PPh3 reacts reluctantly with the alkoxy anion to give CpRuH(PPh3), in contrast to CpRuCl(PPh3)2, which undergoes very facile transformation into CpRuH(PPh3)2.The structure of CpRuCl(CO)PPh3 has been determined by the single-crystal X-ray diffraction method.The compound is triclinic, space group P, a 9.378(2), b 10.584(2), c 16.590(4) Angstroem, α 126.11(1), β 55.91(1), γ 101.49(1) deg .The unit cell contains both R and S enantiomers.A shorter distance of the Ru-Cl bond has been noted in CpRuCl(CO)PPh3 (2.396 Angstroem) in comparison with the Ru-Cl distance in CpRuCl(PPh3)2 (2.453 Angstroem).This causes a diminishing tendency to lose a chloride ion and as a result, nucleophilic attack of RO- on CpRuCl(CO)PPh3.
CYCLOPENTADIENYL-RUTHENIUM AND -OSMIUM COMPLEXES III. CHEMICAL MECHANISM OF DISSOLUTION OF CHLORO(η-CYCLOPENTADIENYL)-BIS(TRIPHENYLPHOSPHINE)RUTHENIUM(II) IN POLAR SOLVENTS
Wilczewski, Tadeusz
, p. 331 - 340 (2007/10/02)
The conversion of CpRuCl(PPh3)2 in boiling ethylene glycol within 90 h of reflux has been investigated.New complex cations in the form of their tetraphenylborates, for which the formulae 1RuCl(PPh3)PPh2Cp2Ru(η-C6H5)>+ and + are proposed, were isolated.The former cation is also formed at lower temperatures during the reflux of CpRuCl(PPh3)2 in methanol.The following process takes place: 2CpRuCl(PPh3)2 -> 1RuCl(PPh3)PPh2Cp2Ru(η-C6H5)>+ + Cl- + 2PPh3.In the presence of dicyclopentadiene during the reflux of CpRuCl(PPh3)2 in high boiling polar solvents (ethylene glycol, dimethyl sulphoxide), ruthenocene is formed in a 90 percent yield.One of the cyclopentadienyl groups in ruthenocene originates from dicyclopentadiene.As a result of the reaction of CpRuCl(PPh3)2 and NaBPh4 in a mixture of diglyme and methanol, a colourless, crystalline compound, CpRu(η-C6H5)BPh3, is obtained in a 50-60 percent yield.
Oxidative cleavage reactions of compounds of the type CpRuLL′R (L, L′ = CO, PPh3; R = Me, PhCH2)
Joseph, Michael F.,Page, John A.,Baird, Michael C.
, p. 1749 - 1754 (2008/10/08)
The compounds CpRuLL′R (Cp = η5-C5H5; L, L′ = CO, PPh3; R = Me, PhCH2) have been prepared, some by improved routes. Alkyl cleavage reactions with halogens, hydrogen chloride, mercury(II) halides, and
ORGANIC CHEMISTRY OF DINUCLEAR METAL CENTRES. PART 7. YLIDES IN THE SYNTHESIS OF ORGANODIRUTHENIUM COMPLEXES : X-RAY CRYSTAL STRUCTURE OF
Davies, David L.,Knox, Selby A. R.,Mead, Kevin A.,Morris, Michael J.,Woodward, Peter
, p. 2293 - 2300 (2007/10/02)
Heating with an ylide Ph3P=CHR in toluene at reflux rapidly yields μ-alkylidene complexes (R = H, 70percent; Me, 35percent; Et, 28percent; or Ph, 57percent).A similar reaction with Ph3P=CHCH=CH2 gives only a 13percent yield of the analogous product , the major product (33percent) being the isomeric substituted allyl complex 3-C3H4-1)(η-C5H5)>.Upon u.v. irradiation the latter undergoes rearrangement, with Ru-Ru bond formation, to give the former, believed to proceed via a 16-electron ?-allyl species.Further u.v. irradiation of releases a CO ligand and brings the alkylidene vinyl substituent into co-ordination, forming in high yield.The two metal atoms in the complex 3-C3H4-1>)(η-C5H5)> are also brought into bonding with one another when the allyl is protonated, yielding the methylvinyl cation +.Treatment of the cation with NaBH4 results in hydride addition to the β-carbon of the vinyl, producing in good yield.The μ-CH2 complex is not formed when and CH2N2 are heated together, but thermally more robust diazoalkanes, CH(CO2Et)N2 and Ph2CN2, afford and respectively.The latter suffers from steric crowding and readily ejects a CO to give , in which a double bond of one phenyl ring is co-ordinated to ruthenium.Under CO pressure this transformation is reversed.The complex is formed in high yield when SO2 is bubbled through a boiling toluene solution of .Crystals of are triclinic, space group , with Z = 2 in a unit cell for which a = 6.771(2), b = 9.315(2), c = 11.864(5) Angstroem, α = 103.12(3), β = 100.61(3), and γ = 103.40(2) deg.The structure has been solved by heavy-atom methods and refined to R 0.0365 (R' 0.0359) for 2 725 independent intensities.The two Ru(CO)(η-C5H5) moieties are held together by a single Ru-Ru bond which is symmetrically bridged by CO and CH2 groups.The interplanar angle between the two bridge systems is 161 deg with the convex side facing the terminal (cis) carbonyl groups.The molecule has idealised Cs (m) symmetry.
A CONVENIENT SYNTHESYIS OF ( RU(η-C5H5)PPh3)(CO)Cl) AND THE CATIONS (Ru(η-C5H5)(PPh3)L(CO))+ (L=CO, PMe3, OR P(OPh)3)
Davies, Stephen G.,Simpson, Stephen J.
, p. 993 - 994 (2007/10/02)
Treatment of (Ru(η-C5H5)(PPh3)Cl) with sulphur under carbon monoxide at 1-3 atm in hot toluene gives quantitative yields of (Ru(η-C5H5)(PPh3)(CO)Cl), which can be further treated in warm methanol with CO, PMe3, and P(OPh)3 to give the cations (Ru(η-C5H5)(PPh3)(CO)2)+, (Ru(η-C5H5)(PPh3)(PMe3)(CO))+, and (Ru(η-C5H5)(PPh3)(P(OPh)3(CO))+ respectively.
