共查询到20条相似文献,搜索用时 375 毫秒
1.
Fernando Hung-Low Gabriela C. Uzcátegui Juan Alvarez Marisol C. Ortega Alvaro J. Pardey Clementina Longo 《Reaction Kinetics and Catalysis Letters》2005,84(1):87-92
Summary Rhodium(I) complexes, [Rh(COD)(amine)2](PF6) (COD = 1,5-cyclooctadiene, amine = 4-picoline, 3-picoline, 2-picoline, pyridine, 3,5-lutidine or 2,6-lutidine) immobilized on poly(4-vinylpyridine) in contact with water catalyzed both the hydroxycarbonylation of 1-hexene to propionic acid and the water-gas shift reaction (WGSR). The role of the coordinated amine on the catalytic activity was examined. 相似文献
2.
Germán Gascón Marisol C. Ortega José D. Suárez Alvaro J. Pardey Clementina Longo 《Reaction Kinetics and Catalysis Letters》2008,94(1):85-89
Rhodium(I) complexes, cis-[Rh(CO)2(amine)2](PF6) (amine = 4-picoline, 3-picoline, 2-picoline, pyridine, 3,5-lutidine or 2,6-lutidine) dissolved in an aqueous solution of
tetrabutylammonium hydrogensulfate (N(C4H9)4HSO4), catalyze the water-gas shift reaction (WGSR). The role of the coordinated amine on the catalytic activity was examined. 相似文献
3.
Alvaro J. Pardey Fernando Hung-Low Gabriela C. Uzcátegui Marisol C. Ortega Clementina Longo 《Reaction Kinetics and Catalysis Letters》2006,88(2):203-208
Summary In this work, a mechanistic study of the hydroxycarbonylation of 1-hexene to heptanoic acid and the water gas shift reaction
(WGSR) catalyzed by the rhodium(I) complexes, [Rh(COD)(amine)2](PF6) (COD = 1,5-cyclooctadiene, amine = 4-picoline, 3-picoline, 2-picoline, pyridine, 3,5-lutidine or 2,6-lutidine) immobilized
on poly(4-vinylpyridine) in contact with water under CO is discussed. Catalytic cycles for these reactions bearing common
Rh-H catalytic species are proposed. 相似文献
4.
Alvaro J. Pardey José Brito María Fernández Angel B. Rivas Marisol C. Ortega Clementina Longo Pablo J. Baricelli Eduardo Lujano Sergio A. Moya 《Reaction Kinetics and Catalysis Letters》2001,74(1):111-118
Reported here is the influence of the reaction conditions variation (1-hexene/rhodium content (S/C) = 16 - 105, temperature (T) = 70 - 110 °C and carbon monoxide pressure (P(CO)) = 0.6 - 1.8 atm) on the catalytic hydroformylation of 1-hexene to aldehydes (heptanal and 2-methyl-hexanal) by the rhodium(I)
complex, [Rh(COD)(2-picoline)2]PF6 (COD = 1,5-cyclooctadiene)immobilized on poly(4-vinylpyridine) in contact with 10 mL of 80% aqueous 2-ethoxyethanol, under
water gas shift reaction condition.
This revised version was published online in June 2006 with corrections to the Cover Date. 相似文献
5.
A. J. Pardey M. Fernández C. Longo E. Lujano P. Baricelli J. Guerrero S. A. Moya 《Reaction Kinetics and Catalysis Letters》1998,65(2):315-320
The activation studies for catalytic reduction of nitrobenzene to aniline by iridium(I) complexes, [Ir(COD)(amine)2]PF6 (COD=1,5-cyclooctadiene, amine =4-picoline, 3-picoline, 2-picoline, or pyridine) heterogenized on poly(4-vinylpyridine) in
aqueous 2-ethoxyethanol are described. The aniline formation (mmol, based on CO2 formed after 9 h) followed the order: 4-picoline (0.068)>2-picoline (0.052)>3-picoline (0.046)≥pyridine (0.042) for 1.0×10−4 mol Ir/0.5 g of polymer, 0.26 mL of nitrobenzene, 10 mL of 2-ethoxyethanol/water, 8/2, v/v, P(CO)=0.9 atm, at 100°C. 相似文献
6.
A. Tiripicchio M.Tiripicchio Camellini C. Claver A. Ruiz L.A. Oro 《Journal of organometallic chemistry》1983,241(1):77-86
The preparation and properties of cationic rhodium complexes of the type [Rh(diolefin)L2]ClO4 (diolefin COD, NBD; L sulfur donor ligand) are described. Pentacoordinated complexes of general formula [Rh(NBD)2L]ClO4 (L SMe2, SEt2, tetrahydrothiophen or trimethylene sulfide) are also reported. The crystal structure of [Rh(NBD)2(Set2)]ClO4 has been determined by X-ray methods. The crystals are rhombohedral, space group R3c, with a 14.530(7) Å and α 77.86(5)° (Z = 6). The structure was solved from diffractometer data by direct and Fourier methods and refined by full-matrix least-squares to R = 0.054 for 937 independent observed reflections. In the cationic [Rh(NBD)2(SEt2)]+ complex the Rh atom is pentacoordinated, the geometry about the metal being a square pyramid whose base is defined by the midpoints of the olefin bonds from two norbornadiene molecules and the apex is occupied by a sulfur atom of the thioether ligand at a rather long distance [Rh?S 2.500(4) Å]. 相似文献
7.
The structure of Rh2(CH3CO2)4(DMF)2 {DMF = HCON(CH3)2} has been determined by single crystal X-ray methods. The compound crystallizes with eight formula units in a cell of dimensions: a = 29.438(7) Å, b = 7.978(2) Å, c = 20.279(5) Å, β = 113.20(4)°, V = 4377.5 Å3, space group C2/c. The structure has been refined by full-matrix least-squares method to a final R = 0.030 for the 4156 observed data. Two Rh(II) atoms are linked by four acetate groups forming a dimeric unit, where the RhRh distance is 2.383(1) Å. The coordination sphere about each Rh atom is completed by a DMF molecule; the average RhO(DMF) distance is 2.296(3) Å. 相似文献
8.
E. A. Shusharina A. A. Rybinskaya P. E. Plyusnin Yu. V. Shubin S. V. Korenev S. A. Gromilov 《Journal of Structural Chemistry》2011,52(3):621-624
An XRD analysis is used to study the single crystal of [Pd(NH3)4][Rh(NH3)(NO2)5] double complex salt at T = 150(2) K. Crystallographic characteristics are as follows: a = 7.6458(5) ?, b = 9.8813(6) ?, c = 9.5788(7) ?, β = 109.469(2)°, V = 682.30(8) ?3, P21/m space group, Z = 2, d
x = 2.553 g/cm3. The geometry of the complex [Rh(NH3)(NO2)5]2− anion is described for the first time: Rh-N(NO2) distances are 2.020(4)–2.060(3) ?, Rh-N(NH3) 2.074(4) ?, N(NO2)-Rh-N(NH3) trans-angle is 178.8(2)°. 相似文献
9.
L.A. Oro M. Esteban R.M. Claramunt J. Elguero C. Foces-Foces F.H. Cano 《Journal of organometallic chemistry》1984,276(1):79-97
The synthesis and properties of neutral and cationic complexes of general formulae [{RhCl(diolefin)}2(CH2(pz)2)], [Rh(CO)2 (CH2(pz)2)][RhCl2(CO)2], (Rh(diolefin)(CH2(pz)2)]ClO2, [{Rh(diolefin)(PPh3)}2(CH2(pz)2)](ClO4)2, [Rh(CO)2(CH2(pz)2)]ClO4 and [Rh(CO)(CH2(pz)2)(PPh3)]ClO4 are described. The NMR spectra of [Rh(COD)(CH2(pz)2)]ClO4 complexes are discussed. X-ray structural analysis of [Rh(COD)(CH2(Pz)2)]ClO4 · C2H4Cl2 is presented; the final R factor is 0.061 for 2436 observed data, recorded with Cu-Kα, not corrected for absorption and with the sample inside a capillary. The Rh atom presents a distorted square planar coordination in a mononuclear arrangement. The COD ring has a twisted boat conformation, and the two halves of the CH2(Pz)2 moiety, which are quite similar to one another, form an angle of 47.2(4)°. 相似文献
10.
The crystal structure of (NH4)2Na[Rh(NO2)6] previously studied only from the data on polycrystals is refined. The selection of the Fm-3 space group is shown to be unambiguous. Geometrical characteristics of the complex [Rh(NO2)6]3s-anion are: Rh—N 2.051 ?, N-O 1.237 ?, ∠O-N-O 119.0°. 相似文献
11.
The thermal decompositions of solid complexes of the type Ni(NCS)2L2 (L = pyridine,α-picoline,β-picoline, 2,6-lutidine, and quinoline) were studied by means of the derivatograph. It was found that the decompositions of complexes with pyridine,α-picoline, 2,6-lutidine, and quinoline (the pseudo-octahedral complex) are onestep processes, and those of complexes withβ-picoline and quinoline (the squareplanar complex) consist of two steps. Diffuse reflectance spectra were recorded to elucidate the structures of the decomposition intermediates. The reasons for the different stoichiometries of decomposition for complexes of the same type are discussed. 相似文献
12.
Davide Collini Serena Fedi Cristina Femoni Francesco Kaswalder Maria Carmela Iapalucci Giuliano Longoni Piero Zanello 《Journal of Cluster Science》2005,16(3):455-476
The reaction of the [Ni6(CO)12]2− dianion with [Rh(COD)Cl]2 (COD = cyclooctadiene) in acetone affords a mixture of bimetallic Ni–Rh clusters, mainly consisting of the new [Ni7Rh3(CO)18]3− and [Ni8Rh(CO)18]3− trianions. A study of the reactivity of [Ni7Rh3(CO)18]3− led to isolation of the new [Ni3Rh3(CO)13]3− and [NiRh8(CO)19]2− anions. All these new bimetallic Ni–Rh carbonyl clusters have been isolated in the solid state as tetrasubstituted ammonium
salts and have been characterised by elemental analysis, X-ray diffraction studies, ESI-MS and electrochemistry. The unit
cell of the [NEt4]3[Ni7Rh3(CO)18] salt contains two orientationally-disordered ν2-tetrahedral [Ni7Rh3(CO)18]3− trianions with occupancy factors of 0.75 and 0.25. Besides, their inner Ni3Rh3 octahedral moieties show two cis sites purely occupied by Rh atoms, two trans sites purely occupied by Ni atoms and the remaining two cis sites are disordered Ni and Rh sites with respective occupancy fraction of 0.5. At difference from the parent [Ni7Rh3(CO)18]3−, the octahedral [Ni3Rh3(CO)13]3− displays an ordered distribution of Ni and Rh atoms in two staggered triangles. The [NiRh8(CO)19]2− dianion adopts an isomeric metal frame with respect to that of the [PtRh8(CO)19]2− congener. As a fallout of this work, new high-yield synthesis of the known [Ni6Rh3(CO)17]3− and [Ni6Rh5(CO)21]3−, as well as other currently-investigated bimetallic Ni–Rh clusters have been obtained. 相似文献
13.
Jia-Sheng Zhang 《Journal of organometallic chemistry》2007,692(18):3944-3948
Two hetero-binuclear complexes [Cp∗CoS2C2(B9H10)][Rh(COD)] (2a) and [Cp∗CoSe2C2(B10H10)][Rh(COD)] (2b) [Cp∗ = η5-pentamethylcyclopentadienyl, COD = cyclo-octa-1,5-diene (C8H12)] were synthesized by the reactions of half-sandwich complexes [Cp∗CoE2C2(B10H10)] [E = S (1a), Se (1b)] with low valent transition metal complexes [Rh(COD)(OEt)]2 and [Rh(COD)(OMe)]2. Although the reaction conditions are the same, the structures of two products for dithiolato carborane and diselenolato carborane are different. The cage of the carborane in 2a was opened; However, the carborane cage in 2b was intact. Complexes 2a and 2b have been fully characterized by 1H, 11B NMR and IR spectroscopy, as well as by elemental analyses. The molecular structures of 2a and 2b have been determined by single-crystal X-ray diffraction analyses and strong metal-metal interactions between cobalt and rhodium atoms (2.6260 Å (2a) and 2.7057 Å (2b)) are existent. 相似文献
14.
Cyclometallation occurs when a solution of the complex Rh(oq)(CO)(PCBr), (PCBr = 2-bromo-3,4,5,6-tetrafluorophenyldiphenylphosphine; OQ = 8-hydroxyquinolinate) in toluene is refluxed, giving
) (PC = P(C6F4)(C6H5)2) and a dimeric compound, not yet completely characterized, formulated as Rh2Br(oq)(PCBr)2.
) was characterized by elemental analysis, by conductance measurements, and by 19F, 31P NMR and infrared spectroscopy. Its molecular structure was determined by single-crystal X-ray methods and refined by standard procedures to final agreement factors R and Rw of 0.067 and 0.060 for 5346 observed data. Lattice constants are 15.8494(6), 14.7188(5), 14.6675(5) Å and β 96.933(3)°, with monoclinic symmetry. The complex has a distorted octahedral geometry with a four atom metallocycle-ring (Rh---P---C---C) showing distorted angles of 69.8(2) and 84.8(2)° at Rh and P atoms, respectively. The analogous compound
), (5-moq = 5-methyl-8-hydroxyquinolinate), can be obtained by heating Rh(5-moq)(CO)(PCBr). 相似文献
15.
Jouni Pursiainen Tapani A. Pakkanen Juhani Jääskeläinen 《Journal of organometallic chemistry》1985,290(1):85-98
A new ruthenium-rhodium mixed-metal cluster HRuRh3(CO)12 and its derivatives HRuRh3(CO)10(PPh3)2 and HRuCo3(CO)10(PPh3)2 have been synthesized and characterized. The following crystal and molecular structures are reported: HRuRh3(CO)12: monoclinic, space group P21/c, a 9.230(4), b 11.790(5), c 17.124(9) Å, β 91.29(4)°, Z = 4; HRuRh3(CO)10(PPh3)2·C6H14: triclinic, space group P, a 11.777(2), b 14.079(2), c 17.010(2) Å, α 86.99(1), β 76.91(1), γ 72.49(1)°, Z = 2; HRuCo3(CO)10(PPh3)2·CH2Cl2: triclinic, space group P, a 11.577(7), b 13.729(7), c 16.777(10) Å, α 81.39(4), β 77.84(5), γ 65.56°, Z = 2. The reaction between Rh(CO)4? and (Ru(CO)3Cl2)2 tetrahydrofuran followed by acid treatment yields HRuRh3(CO)12 in high yield. Its structural analysis was complicated by a 80–20% packing disorder. More detailed structural data were obtained from the fully ordered structure of HRuRh3(CO)10(PPh3)2, which is closely related to HRuCo3(CO)10(PPh3)2 and HFeCo3(CO)10(PPh3)2. The phosphines are axially coordinated. 相似文献
16.
Jordi Garc?&#x;a-Antón René Mathieu Noël Lugan Josep Ros 《Journal of organometallic chemistry》2004,689(9):1599-1608
The 1,5-bis(3,5-dimethyl-1-pyrazolyl)-3-thiapentane ligand (bdtp) reacts with [Rh(COD)(THF)2][BF4] to give [Rh(COD)(bdtp)][BF4] ([1][BF4]), which is fluxional in solution on the NMR time scale. Its further treatment with carbon monoxide leads to a displacement of the 1,5-cyclooctadiene ligand, generating a mixture of two complexes, namely, [Rh(CO)2(bdtp)][BF4] ([2][BF4]) and [Rh(CO)(bdtp-κ3N,N,S)][BF4] ([3][BF4]). In solution, [2][BF4] exists as a mixture of two isomers, [Rh(CO)2(bdtp-κ2N,N)]+ ([2a]+) and [Rh(CO)2(bdtp-κ3N,N,S)]+ ([2b]+; major isomer) rapidly interconverting on the NMR time scale. At room temperature, [2][BF4] easily loses one molecule of carbon monoxide to give [3][BF4]. The latter is prone to react with carbon monoxide to partially regenerate [2][BF4]. The ligands 1,2-bis[3-(3,5-dimethyl-1-pyrazolyl)-2-thiapropyl]benzene (bddf) and 1,8-bis(3,5-dimethyl-1-pyrazolyl)-3,6-dithiaoctane (bddo) are seen to react with two equivalents of [Rh(COD)(THF)2][BF4] to give the dinuclear complexes [Rh2(bddf)(COD)2][BF4]2 ([4][BF4]2) and [Rh2(bddo)(COD)2][BF4]2 ([5][BF4]2), respectively. In such complexes, the ligand acts as a double pincer holding two rhodium atoms through a chelation involving S and N donor atoms. Bubbling carbon monoxide into a solution of [4][BF4]2 results in loss of the COD ligand and carbonylation to give [Rh2(bddf)(CO)4][BF4]2 ([6][BF4]2). The single-crystal X-ray structures of [3][CF3SO3], [5][BF4]2 and [6][BF4]2 are reported. 相似文献
17.
Bruno Crociani Umberto Belluco Pierluigi Sandrini 《Journal of organometallic chemistry》1979,177(2):385-401
The reactions of the organometallic 1,4-diazabutadienes, RN=C(R′)C(Me)=NR″ [R = R″ = p-C6H4OMe, R′ = trans-PdCl(PPh3)2 (DAB); R = p-C6H4OMe, R″ = Me, R′ = trans-PdCl(PPh3)2 (DABI; R = R″ = p-C6H4OMe, R′ = Pd(dmtc)-(PPh3), dmtc = dimethyldithiocarbamate (DABII); R = R″ = p-C6H4OMe, R′ = PdCl(diphos), diphos = 1,2-bis(diphenylphosphino)ethane (DABIII)] with [RhCl(COD)]2 (COD = 1,5-cyclooctadiene, Pd/Rh ratio = ) depend on the nature of the ancillary ligands at the Pd atom in group R′. In the reactions with DAB and DABI transfer of one PPh3 ligand from Pd to Rh occurs yielding [RhCl(COD)(PPh3)] and the new binuclear complexes [Rh(COD) {RN=C(R?)-C(Me)=NR″}], in which the diazabutadiene moiety acts as a chelating bidentate ligand. Exchange of ligands between the two different metallic centers also occurs in the reaction with DABII. In this case, the migration of the bidentate dmtc anion yields [Rh(COD)Pdmtc] and [Rh(COD) {RN=C(R?)C(Me)=NR″}]. In contrast, the reaction with DABIII leads to the ionic product [Rh(COD)- (DABIII)][RhCl2(COD)], with no transfer of ligands. The cationic complex [Rh(COD)(DABIII)]+ can be isolated as the perchlorate salt from the same reaction (Pd/Rh ratio = 1/1) in the presence of an excess of NaClO4. In all the binuclear complexes the coordinated 1,5-cyclooctadiene can be readily displaced by carbon monoxide to give the corresponding dicarbonyl derivatives. The reaction of [RhCl(CO)2]2 with DAB and/or DABI yields trinuclear complexes of the type [RhCl(CO)2]2(DAB), in which the diazabutadiene group acts as a bridging bidentate ligand. Some reactions of the organic diazabutadiene RN=C(Me)C(Me)=NR (R = p-C6H4OMe) are also reported for comparison. 相似文献
18.
Michael I. Bruce Trevor W. Hambley MichaeL R. Snow A.Geoffrey Swincer 《Journal of organometallic chemistry》1982,235(1):105-112
The title complex was obtained from the adduct of C2(CN)4 and Rh(CCPh)-(CO)(PPh3)2 by simple substitution of CO in refluxing acetonitrile. Crystals of the complex are orthorhombic, with a 10.058(2), b 20.008(4), c 21.594(5) Å, space group P212121, Z 4. The rhodium has approximate trigonal bipyramidal coordination, with apical NCMe and C2Ph ligands: RhC2Ph, 1.939(18); RhC(olefinic), 2.151, 2.157(19); RhN, 2.051(16); RhP, 2.377, 2.397(6) Å. 相似文献
19.
T. E. Kokina L. A. Glinskaya E. A. Sankova R. F. Klevtsova S. V. Larionov 《Journal of Structural Chemistry》2005,46(6):1031-1038
The interaction of the Co(iso-Bu2PS2)2 chelate with 4-NH2Py afforded a paramagnetic complex [Co(4-NH2Py)(iso-Bu2PS2)2] (μeff = 4.53 BM). Single crystals of [Ni(4-NH2Py)2(iso-Bu2PS2)2] (I) and [Co(4-NH2Py)(iso-Bu2PS2)2] (II) were grown and used for X-ray diffraction investigation (X8 APEX diffractometer, MoK
α radiation). Crystals I are monoclinic with unit cell parameters a = 12.5336(5) Å, b = 9.4356(4) Å, c = 16.4095(6) Å; β = 111.351(1)°; V = 1807.4(1) Å3; Z = 2, ρ = 1.223 g/cm3, space group P21/n. Crystals II are triclinic with unit cell parameters a = 8.7572(4) Å, b = 9.6934(6) Å, c = 18.665(1) Å; α = 79.374(2)°, β = 87.049(2)°, γ = 75.640(2)°; V = 1508.6(1) Å3; Z = 2, ρ = 1.259 g/cm3; space group
. The structures of I and II are formed by isolated mononuclear molecules. The coordination unit is NiN2S4 (octahedron) in I and CoNS4 (tetragonal pyramid) in II. The 4-NH2Py molecule is coordinated through the N atom of the heterocycle. Electronic spectroscopy data for II agree with the symmetry of the NS4 polyhedron found by X-ray diffraction (XRD) analysis. The noncoordinated amine groups link the complex molecules via N-H...S
hydrogen bonds.
__________
Translated from Zhurnal Strukturnoi Khimii, Vol. 46, No. 6, pp.1072–1080, November–December, 2005.
Original Russian Text Copyright ? 2005 by T. E. Kokina, L. A. Glinskaya, E. A. Sankova, R. F. Klevtsova, and S. V. Larionov 相似文献
20.
C5Me5Rh(L)P2Me4 (L = CO, C2H4) reacts with [C5Me5Rh(μ-CO)]2, to give the trinuclear complexes C5Me5(L)Rh(μ-P2Me4)RhC5Me5(μ-CO)2RhC5Me5 (VI, VII). In the reactions of C5Me5Rh(CO)P2Me4 with C5H5(CO)2 (M = Rh, Co) and C5H4RMn(CO)3 (R = H, Me), the homo- and hetero-metallic binuclear compounds C5Me5(CO)Rh(μ-P2Me4)M(CO)C5H5 (VIII, IX) and C5Me5(CO)Rh(μ-P2Me4)Mn(CO)2C5H4R (X, XI) are obtained in almost quantitative yield. The X-ray structure of the complex C5Me5[P(OMe)3]Rh(μ-CO)2RhC5Me5 (III), which is structurally related to VI and VII, has been determined. The molecule contains an unsymmetrical, non-planar Rh2C2-skeleton with different Rh-C(O) bond lengths. The Rh-Rh distance is 268.5(1) pm; the planes of the two five-membered rings form an angle of 62.6°. 相似文献