14285-68-8Relevant articles and documents
Coupling and annelation of two acetylide groups and alkyne molecules in the reaction of (OC)5ReCCPh with ferrocenylacetylene. Crystal and molecular structure of Re2(CO)7*acetone
Koridze, A.A.,Zdanovich, V.I.,Kizas, O.A.,Yanovsky, A.I.,Struchkov, Yu.T.
, p. 197 - 202 (1994)
X-Ray diffraction study was carried out of the binuclear complex Re2(CO)7(C8H2Ph2Fc2) (II), obtained in the reaction of (OC)5ReCCPh with ferrocenylacetylene FcCCH in refluxing toluene.Complex II crystallizes in the monoclinic space group P21/n with a 20.363(5), b 10.121(2), c 22.952(7) Angstroem, β 112.49(2)o, V 4302(2) Angstroem3, and Z=4.Compound II possesses a rhenacyclopentadiene ring, fused with the methylenecyclopentene moiety along the central C-C bond, and ?-bonded by the Re(CO)3 group.The hydrocarbon ligand of compound II is formed by condensation of two PhCC groups and two FcCCH molecules.Preparative methods of synthesis of (OC)5ReCCPh, (OC)5ReCCCO2Me and (OC)5ReCCSiMe3 are reported. Key words: Rhenium; Ferrocene; Alkyne; Carbonyl; Crystal structure
SYNTHESIS AND X-RAY STRUCTURE OF PENTACARBONYL(7-η1-CYCLOHEPTA-1,3,5-TRIENYL)RHENIUM(I)
Heinekey, D.Michael,Graham, William A.G.
, p. 335 - 344 (1982)
Synthesis by two routes of (7-η1-C7H7)Re(CO)5 (2), the first monohaptocycloheptatrienyl derivative of a transition metal, is described.The first involves ultraviolet irradiation of the acyl C7H7(CO)Re(CO)5 (1) in acetone at -78 deg C.The second and preferred route involves reaction of NaRe(CO)5 with in THF to form orange crystalline 2 in 90percent yield.Activation enthalpy for thermal decomposition of 2 to form ditropyl and Re2(CO)10 is 30.4 +/- 0.3 kcal mole-1, a value close to the estimated strength of the C7H7-Re(CO)5 bond.A single crystal X-ray diffraction study of 2 shows a nearly octahedral Re(CO)5 group bonded in the quasi-axial position to the methylene carbon atom of the seven-membered ring, which has a boat conformation.NMR spectra are consistent with a similar structure as the exclusive or dominant form in solution.
Phenylacetylene transformations in clusters with Re2Fe and Re2Ni2 core. Synthesis and molecular structure of Re2Fe(CO)9(μ3,η4-CH=CHC6H4) and Cp2Ni2Re2(CO)6(μ4-PhCCCH=CHPh)
Shaposhnikova, A. D.,Kamalov, G. L.,Stadnichenko, R. A.,Pasynskii, A. A.,Eremenko, I. L.,et al.
, p. 111 - 120 (1991)
Interaction of the binuclear complex Re2(CO)8(μ-H)(μ-CCPh) (I) with Fe3(CO)12 and Cp2Ni has been studied.Reaction of I with Fe3(CO)12 in refluxing toluene results in formation of a heterometallic cluster Re2Fe(CO)9 (μ3,η4-CH=CH-C6H4) (II).According to the X-ray structural data, in this cluster ortho-metallation of the phenyl ring occurs and results in the appearance of the metalcyclopentadiene fragment.The core of the cluster II is an angular metal chain Re2Fe with equal Re-Fe bond lengths of 2.671(2) Angstroem and nonbonding Re(1)Re(2) distances of 3.893(7) Angstroem.Reaction of I with Cp2Ni in refluxing o-xylene results in formation of the heterometallic cluster Cp2Ni2Re2(CO)6(μ4-PhCCCH=CHPh) (III) (70percent) along with the trinuclear cluster Cp3Ni3(μ-CO)2 and Re2(CO)10.According to the X-ray structural data cluster III contains a heterometallic Re2Ni2 butterfly core with a dihedral angle of 122 deg between the Re2Ni planes.Dimerisation of the two acetylene fragments gives a ligand which is coordinated between the ReNi2 wings only by a CC triple bond (with the length of 1.48(2) Angstroem), the second hydrocarbon fragment CH=CHPh is non-coordinated.
RHENIUM CARBONYL AND DINITROGEN COMPLEXES: IDENTIFICATION OF INTERMEDIATES BY MATRIX ISOLATION PHOTOCHEMISTRY AND METAL ATOM SYNTHESIS
Klotzbuecher, W. E.
, p. 5 - 10 (1988)
Mono- and dinuclear rhenium species were produced by irradiation of Re2(CO)10 in inert and reactive matrices and by direct synthesis of novel compounds via cocondensation of rhenium atoms with prospective ligands (N2, O2, 13CO, C2H4, H2O).Subtle differenc
Coordination chemistry of thioether-carboranes in polynuclear metal carbonyl cluster complexes. B-H activation of thioether-carboranes by dirhenium carbonyl complexes
Adams, Richard D.,Kiprotich, Joseph
, p. 23 - 28 (2018)
Two new dirhenium compounds Re2(CO)8[μ-η2-1,3-C2B10H10(1-SCH3)](μ-H), 1 (3.2 % yield) and Re2(CO)8[μ-η2-1,4-C2B10H10(1-SCH3)](μ-H), 2 (31 % yield) were obtained from the reaction of closo-o-(1-SCH3)C2B10H11 with Re2(CO)8[μ-η2-C(H)C(H)Bun](μ-H) in an octane solution heated to reflux. Both compounds contain a C2B10H10(1-SCH3) ligand that bridges the pair of rhenium atoms by the sulfur atom and one of the boron atoms of the carborane cage. The Re – B bonds were formed by oxidative addition of one of the B – H bonds of the carborane to one of the Re atoms. The isomers differ by which boron atom, B(3) for 1 and B(4) for 2, has been added to the Re atom. Compound 1 was isomerized to 2 by heating to 107 °C, but 2 does not isomerize back to 1. A mechanism for the isomerization that involves a reductive-elimination of B(3) and the hydride ligand of 1 followed by an oxidative-addition of the neighboring B(4)-H bond to form 2 is proposed. The new compound Re2(CO)7[μ-η3-C2B10H9(1,2-(SCH3)2](μ-H), 3 was obtained in 38% yield from the reaction of [o-1,2-(SCH3)2]C2B10H10 with Re2(CO)8[μ-η2-C(H)C(H)Bun](μ-H) in an octane solution heated to reflux for 2h. The bridging C2B10H9(1,2-(SCH3)2 ligand is coordinated to one of the rhenium atoms by the two sulfur atoms at one of the Re atoms and the carborane boron atom B(3) also underwent cleavage at the B(3) – H bond to form the Re – B(3) bond to the other Re atom.
Rapid and mild synthesis of [Re2(CO)10] by reduction of [NH4][ReO4] at atmospheric CO pressure
Top, Siden,Morel, Pierre,Pankowski, Marek,Jaouen, Gerard
, p. 3611 - 3612 (1996)
With a view to accessing radiopharmaceuticals based on 186Re and 188Re, a simple, efficient and rapid synthesis at low CO pressure of the key complex [Re2(CO)10] from [NH4][ReO4] using (Me2CHCH2)2AlH in toluene as reducing agent has been obtained. Copyright 1996 by the Royal Society of Chemistry.
DIRHENIUM COMPLEXES CONTAINING LINKED DIPHENYLACETYLENE MOLECULES FROM THE PHOTOREACTION OF H3Re3(CO)12 WITH PhCPhC. CRYSTAL AND MOLECULAR STRUCTURES OF Re2(CO)5(C4Ph4)(C2Ph2) AND Re2(CO)4(C6Ph6)(C2Ph2)*0.5 HEXANE
Pourreau, Daniel B.,Whittle, Robert R.,Geoffroy, Gregory L.
, p. 333 - 346 (1984)
Photolysis of H3Re3(CO)12 in presence of diphenylacetylene (DPA) yields Re2(CO)10, HRe(CO)5, and the three alkyne complexes Re2(CO)7(DPA)2, Re2(CO)5(C4Ph4)(DPA) (4) and Re2(CO)4(C6Ph6)(DPA) (3), the latter two which were shown by X-ray crystallography to possess linked DPA ligands.The complex Re2(CO)5(C4Ph4)(DPA) crystallizes in the triclinic space group P (No.2) with a 11.277(3), b 12.301(3), c 14.851(3) Angstroem, α 97.37(2), β 104.68(2), γ 104.49(2) deg, V 1889(2) Angstroem3, and Z = 2.The structure was refined using the 4548 reflections with I 2?(I) to give final residuals of R = 0.031 and Rw = 0.041.Complex 4 possesses a rhenacyclopentadiene group bonded to the second rhenium atom and an η2-DPA ligand bound to the rhenium atom of the metallacycle.The complex Re2(CO)4(C6Ph6)(DPA) crystallizes in the monoclinic space group P21/c (No.14) with a 17.048(4), b 16.676(2), c 18.569(4) Angstroem, β 106,70(2) deg, V 5056(3) Angstroem3, and Z = 4.For the 3568 reflections with I 2?(I), the structure refined to R = 0.078 and Rw = 0.074.Three of the DPA molecules in Re2(CO)4(C6Ph6)(DPA) are linked together to form a fly-over bridge between the two rhenium atoms.The fourth DPA molecules is η2-bound to one rhenium center.
Structure and dynamics of the η2-hexafluorobenzene complexes [Re(η5-C5H4R)(CO)2(η 2-C6F6)] (R = H or Me) and [Rh(η5-C5Me5)(PMe3)(η 2-C6F6)]
Higgitt, Catherine L.,Klahn, A. Hugo,Moore, Madeleine H.,Oelckers, Beatriz,Partridge, Martin G.,Perutz, Robin N.
, p. 1269 - 1280 (1997)
Photolysis of [Re(η5-C5H4R)(CO)3] (R = H or Me) in hexafluorobenzene yielded [Re(η5-C5H4R)(CO)2(η 2-C6F6)] containing the η2-co-ordinated arene. The complex containing η2-C5H5 has been characterised crystallographically. It forms monoclinic crystals in space group P21ln with Z = 4, a = 7.926(2), b = 12.179(4), c = 13.675(4) A and β = 102.91(2)°. The structure reveals the expected features of distortion of the C6F6 unit from planarity at the co-ordinated C-C bond; The rhenium lies 2.059(7) A from the mid-point of the co-ordinated C-C bond of C6F6. The IR and low-temperature 19F NMR spectra reveal the presence of two rotamers, which are interconverted by rotation about the metal-C6F6 bond with ΔG? = 36.7 kJ mol-1 at 184 K. At higher temperatures a second intramolecular rearrangement causes broadening of the 19F resonances. This fluxional process has been identified as a [1,2]-shift of the site of rhenium co-ordination by linewidth and exchange spectroscopy measurements: ΔH? = 57.6 ± 0.5 kJ mol-1, ΔS? = -7 ±2 J K-1 mol-1. The dynamic behaviour of the (η5-C5H4Me) complex is extremely similar. The crystal structure of [Rh(η5-C5Me5)(PMe3)(η 2-C6F6)], synthesised previously, has been determined for comparison. It crystallises in the same space group with a = 8.694(9), b =16.818(9), c = 14.642(6) A and β = 106.69(6)°. The structural features of this rhodium complex are very similar to the rhenium complex, but the metal lies 1.920(5) A from the mid-point of the co-ordinated C-C bond of the C6F6 unit. The shortening of the M-C6F6 bond is associated with the stereochemical rigidity of this complex. The C-F bonds of the co-ordinated carbons atoms are 0.049(7) A longer than the remaining C-F bonds. Comparison of structural features of three η2-C6F6 complexes revealed ,that the distortions of the C6F6 unit are almost constant, indicating a hard potential-energy surface. The analogy to co-ordinated C2F4 is reinforced by the similarity in co-ordination geometry. The electron-withdrawing character of η2-C6F6 is confirmed by the v(CO) frequencies of [Re(η5-C5H5)(CO)2(η 2-C6F6)] which lie at the high limit for complexes of the type [Re(η5-C5H5)(CO)2L].
Improved synthesis of carbonylrhenium
Crocker, Lisa S.,Gould, George L.,Heinekey, D. Michael
, p. 243 - 244 (1988)
An improved procedure for the preparation of Re2(CO)10 is reported.Carbonylation of methanol solutions of NaReO4 (3200 psi, 230 deg C, 48 h) in the presence of a metallic copper catalyst affords Re2(CO)10 in 90 percent yield.
Mechanism of Re2(CO)10 Substitution Reactions: Crossover Experiments with 185Re2(CO)10 and 187Re2(CO)10
Stolzenberg, A.M.,Muetterties, E.L.
, p. 822 - 827 (1983)
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.
