51371-62-1

Upstream product

• 14285-68-8 decacarbonyldirhenium⁽⁰⁾ 
• 603-35-0 triphenylphosphine 
• 33634-75-2 sodium pentacarbonylrhenate 
• 70083-75-9 pentacarbonyl(triphenylphosphane)rhenium tetrafluoroborate 
• 83214-31-7 eq-aquadirhenium nonacarbonyl 

Downstream Products

• 15189-55-6 cis-[Re(CO)4I(PPh₃)] 
• 14285-68-8 decacarbonyldirhenium⁽⁰⁾ 
• 96041-49-5 (.mu-H)(μ-CH=CH2)Re2(CO)7(PPh3) 
• 96041-51-9 HRe₂(CO)6(CHCH₂)(P(C₆H₅)3)2 
• 142560-47-2 cis-[Re(CO)4Br(PPh₃)] 

Relevant academic research and scientific papers

Oxygen atom transfer reactions to metal carbonyls: Kinetics and mechanism of CO substitution reactions of M2(CO)9L (M=Re, L=PPh 3, PMePh2, PMe2Ph, C5H5N, or M=Mn, L=C5H5N) in the presence of (CH 3)3NO

Rates for the reactions of M2(CO)9L (M = Re, L = PPh3, PMePh2, PMe2Ph, C5H 5N or M = Mn, L = C5H5N) with L in the presence of (CH3)3NO as O-atom transfer reagent and CHCl 3 as solvent are reported. The reaction rates suggest a pathway of association (k2). The reaction rate order of Re2(CO) 9L with the four ligands is as follows: PPh3 > PMePh2 > PMe2Ph > C5H5N.

Substituted metal carbonyls. 26.1 One-step synthesis, structures, NMR, and dynamic laser-light scattering of Re2(μ-OMe)2[μ-Ph2P(CH2) nPPh2](CO)6 (n = 1-4)

Oxidative decarbonylation of Re2(CO)10 by Me3NO in a mixture of THF and MeOH followed by addition of alkyl-chained diphosphine Ph2P(CH2)nPPh2 (PP) (n = 1-4) gives Re2(μ-OMe)2-(μ-PP)(CO)6 in 34, 29, 28, and 10% yields, respectively. This methanolytic oxidation across the Re-Re bond provides a general and one-step route for the synthesis of these dirhenium hexacarbonyl complexes with diphosphine and methoxo bridges. The molecular structure of Re2(μ-OMe)2(μ-Ph2PCH2PPh 2)(CO)6 was determined by single-crystal X-ray diffraction analysis. It contains two fac-[Re(CO)3] moieties bridged by dppm and two methoxo ligands. The {Re2O2} core is significantly more planar than that in the Fe(C5H4PPh2)2 analogue. That such a dinuclear core is maintained in spite of the different steric demands of the different bridging diphosphines illustrates the great geometric tolerance of the bridging methoxo groups. The fluxionality of the dppm, dppe, and dppp complexes has been studied and compared by molecular modeling and solution 1H NMR spectroscopy. Dynamic laser-light scattering (DLS) shows that the dppe complex aggregates in CH2Cl2 to form small clusters with an average radius of ～370 nm. The use of a combination of DLS and NMR in organometallic chemistry is unprecedented.

Kinetics and Mechanism of CO Substitution of M2(CO)10 (M = Mn, Re) with an Entering Ligand (PPh3 or Py) in the Presence of an O-Atom Transfer Reagent (Me3NO or (CH3OC6H4)2TeO)

Detailed kinetic data are reported for the CO substitution of M2(CO)10 ( M = Mn, Re) with PPh3 or Py in the presence of Me3NO or (CH3OC6H4)TeO as an O atom transfer reagent in CHCl3 solvent.The rates of reactions are first order in concentrations of M2(CO

Metallorganische Lewis-Saeuren. XXXVII. Kationische Pentacarbonyl(phosphan)rhenium-komplexe und deren Reactionen mit Nucleophilen

The raections of pentacarbonyltetrafluoroboratorhenium, (OC)5ReFBF3, with PH3, PPh3, PPh2H, and chlorphosphanes lead to cationic complexes +BF4- (1).Nucleophiles react with the chlorphosphane ligands of 1 to give the ionic complexes +BF4- (R'=OH, OMe, OEt).Reaction of +BF4- with OH- yields the bridged 2+2BF4-, whereas with +BF4- and OH- the complex +BF4- is formed.The azide ion is added to a cis-carbonyl ligand of +BF4- to form the neutral isocyanato complex (OC)4(ClPh2P)ReNCO.The hydroxycarbonyl complexes cis-(OC)4Re(PPh2R)(COOH) are obtained from the reaction of +BF4- (R=Ph, H) with hydroxide.The reactions of + with M(CO)5- (L=PPh3, P(OMe)3, CN-tBu; M=Mn, Re) give the nonacarbonyl dimetal compounds L(OC)4Re-M(CO)5.

The Palladium-catalysed Reaction Between and Phosphines and the Crystal and Molecular Structure of Diaxial

The reaction between and PR3 in xylene is catalysed by Pd/C, Pd/CaCO3, and PdO and yields the complexes 10-n(PR3)n> (n=1 or 2) as the major products (15-80percent).Attempts to synthesise 10-n(PR3)n from and PR3 in the presence of NMe3O under milder conditions (e.g. refluxing CH2Cl2) also gave the above products with n=1 or 2 as well as high yields of fac-.An X-ray crystal structure determination of diaxial was carried out: space group C2/c, Z=4, a=22.779(9), b=7.166(3), c=17.249(7) Angstroem, β=95.13(3) deg, R=0.0602.The structure has a staggered geometry with torsion angles deviating by +/-6 deg from the ideal (45 deg).The Re-Re bond length was found to be 3.044(1) Angstroem, cf., 3.041(1) Angstroem for , indicating that this parameter is almost invariant on substitution of CO by PMe2Ph.

Mechanism of Re2(CO)10 Substitution Reactions: Crossover Experiments with 185Re2(CO)10 and 187Re2(CO)10

185Re2(CO)10 and 187Re2(CO)10 were prepared separately and then utilized in combination in crossover experiments to probe for fragmentation to mononuclear rhenium species in thermal and photochemically initiated substitution reactions.For the CO-Re2(CO)10 exchange reaction, a reaction separately analyzed for 13CO-12CO interchange, no crossover was observed at 150 deg C after 14 half-lives of reaction (14 h).Similarily, the thermal reaction sequences of Re2(CO)10 + P(C6H5)3 = Re2(CO)9P(C6H5)3 + CO and Re2(CO)9P(C6H5)3 + P(C6H5)3 = Re2(CO)82 + CO were examined at 150 deg C (maintaining a CO pressure of ca. 560-640 mm).No crossover was detectable in either Re2(CO)10 or Re2(CO)9P(C6H5)3 (relative to blank experiments).Hence, phosphine substitution reactions proceed without a detectable formation of mononuclear rhenium species.These observations support a CO dissociative mechanism.A model based upon this mechanism can accurately reproduce the mass spectra observed during 13CO-12CO interchange.In the absence of a CO atmosphere, 185Re2(CO)10 and 187Re2(CO)10 formed 185Re187Re(CO)10 and this interchange was nearly complete at 150 deg C within 14-16 half-lives.All photochemically initiated reactions with the two labeled decacarbonyls led to complete crossover within short reaction times.It appears then that the primary mode of reaction for Re2(CO)10 under photolysis conditions involves Re-Re bond scission as an early elementary step.Also, the reversible steps leading to the precursor(s) to Re2(CO)10 decomposition include scission of the rhenium-rhenium bond.

Photochemical Reaction of Dirhenium Decacarbonyl with Water

The photochemical reaction of Re2(CO)10 with H2O in THF and other solvents has been studied, with use of radiation of varying wavelength.The initial reaction leads to Re2(CO)9(OH2), formed upon irradiation at 313 nm.This product is shown to form via a pri

FREE RADICAL INTERMEDIATES IN THE REACTION BETWEEN DECACARBONYLDIRHENIUM AND TRIPHENYLPHOSPHANE

The reaction between Re2(CO)10 and PPh3 in refluxing xylene has been re-examined.The main products are 1,2-diaxial Re2(CO)8(PPh3)2 and mer-trans-HRe(CO)(PPh3)2.A range of other products have been isolated by chromatographic procedures and their production rationalised.The previously reported isolable paramagnetic products have not been confirmed, but evidence is presented for their formation as unstable intermediates.