共查询到20条相似文献,搜索用时 15 毫秒
1.
Isabel Moldes Sergeï Nefedov Noël Lugan Ren Mathieu 《Journal of organometallic chemistry》1995,490(1-2):11-19
The reaction of K[H6ReL2] with [RuHCl(CO)(PPh3)3−x {P(OPri}3)x](L2 = (PMePh2)2, dppe, (AsPh3)2, or (PPh3)2; x = 0, 1 or 2) leads to [L2(CO)HRe(μ-H)3RuH(PPh3)2−y{P(OPri)3}y] (x = 0 or 1, Y = 0; X = 2, Y = 1(L2 = PPh3)) in a first step. Under the reaction conditions most of these complexes react rapidly with the liberated phosphine giving [L2(CO)Re(μ-H)3Ru(PPh3)3−y- {P(OPri)3}y] (L2 = (PMePh2)2 or dppe, Y = 0; L2 = (PPh3)2, Y = 1) as the only iso complexes. The structure of [(PMePh2)2(CO)Re(μ-H)3Ru(PPh3)3] has been establishedby X-ray structure analysis. The complex [(PPh3)2(CO)Re(μ-H)3Ru(PPh3)2(P(OPri)3)] reacts with molecular hydrogen under pressure to generate [L2(CO)HRe(μ-H)3RuH(PPh3)(P(OPri)3) as the sole product. 相似文献
2.
The reaction of [(CO)PPh3)2Re(μ-H)2(μ-NCHPh)Ru(PPh3)2(PhCN)] (2) with HBF4-Me2O generates [(CO)PPh3)2Re(μ- H)2(μ,η1,η2HNCHPh)Ru(PPh3)2(PhCN)][BF4] (3). Monitoring the reaction by NMR spectroscopy shows the intermediate formation of [(CO)(PPh3)2 HRe(μ-H)2(μ-NCHPh)Ru(PPh3)2(PhCN)][BF4] (4). Attempted reduction of the imine ligand by a nucleophile (H− or CN−) failed, regenerating 2. Under dihydrogen at 50 atm, 3 is slowly transformed into [(CO)(PPh3)2HRe(μ-H)3Ru(PPh3)2(PhCN)][BF4] (5) with liberation of benzyl amine. 相似文献
3.
Pentacarbonyl(diethylaminocarbyne)chromium tetrafluoroborate, [(CO)5− CrCNEt2]BF4 (I), reacts with PPh3 with substitution of CO and formation of trans-tetracarbonyl(diethylaminocarbyne)triphenylphosphanechromium tetra-fluoroborate, trans-[PPh3(CO)4CrCNEt2]BF4 (III). Substitution of CO by PPh3 in neutral trans-tetracarbonyl(halo)(diethylaminocarbyne)chromium complexes, trans-X(CO)4CrCNEt2 (IVa: X = Br, IVb: X = I), leads in a reversible reaction to the corresponding tricarbonyl complexes, mer-X(PPh3)(CO)3− CrNEt2 (V), PPh3 occupying the cis-position to the carbyne ligand. With PPh3 in large excess both reactions follow a first-order rate law. This as well as the activation parameters (ΔH≠ = 104–113 kJ mol−1, ΔS≠ = 64–71 J mol−1 K−1) indicate a dissociative mechanism. 相似文献
4.
The reaction of K[ReH6(PPh3)2] with [RhCl(CO)L2] [L= PPh3, 1,2,5-triphenylphosphole (TPP), or P(OMe)3] leads to the new electronically unsaturated heterobimetallic polyhydride complexes [(CO)(PPh3)2HRe(μ-H)3RhL2] in moderate-to-good yields. The structures of these complexes have been established on the basis of spectroscopic data, especially 1H and 31P NMR. The bridging hydride ligands are fluxional but there is either a slow or nonexistent exchange between terminal and bridging hydrides. For L = PPh3 or TPP, protonation with tetrafluoroboric acid affords quantitatively the cationic complexes [(CO)(PPh3)2HRe(μ-H)3RhHL2]+, isolated as the BF4− or the BPh4− salts. 相似文献
5.
Quanyuan Hu Man Fung Lo Ian D. Williams Naoko Koda Yuko Uchimaru Guochen Jia 《Journal of organometallic chemistry》2003,670(1-2):243-247
Treatment of [Cp*Ru(dppe)]+ with B-triethynyl-N-trimethylborazine and piperidine produces the trimetallic complex [Cp*Ru(dppe)(CC)]3B3N3Me3, the structure of which has been confirmed by X-ray diffraction. Reaction of RuHCl(CO)(PPh3)3 with B-triethynyl-N-trimethylborazine produces the trimetallic complex [RuCl(CO)(PPh3)2(CH=CH)]3B3N3Me3. 相似文献
6.
G. J. Gainsford J. M. Guss P. R. Ireland R. Mason
C. W. Bradford
R. S. Nyholm
《Journal of organometallic chemistry》1972,40(2):C70-C72The structures of HOs3(CO)7(PPh2)(PPh3)(C6H4), HOs3(CO)8(PPh3)(PPh2C6H4) and HOs3(CO)7(PPh2)(PPh2C6H4C6H3) are described, the latter illustrating an intracluster reaction of the coordinated benzyne ligand. 相似文献
7.
4-Vinyl pyridine (4-Vp) reacts with RuHClCO(PPh3)3 (I) in THF to give RuHClCO(PPh3)2(4-Vp) (II, which reacts with sodium derivatives of bidentate chelating ligands to afford substitution products, [RuH(CO)(PPh3)2(L)]. The bindentate ligands used are 2-hydroxybenzaldehyde, 2-hydroxy-3-methoxybenzaldehyde, trifluorothenoylacetone and 8-hydroxyquinoline. Insertion reactions of the Ru---H bond of II with activated olefins such as acrylonitrile [giving RuCl(CO)(CH3CHCN)(PPh3)2(4-Vp)], 2-vinyl pyridine, dimethyl fumarate and monobromodiethyl fumarate have been carried out to obtain chelated Ru---C bonded complexes. RuCl2(PPh3)3 reacts with an excess of 4-Vp to give an octahedral ruthenium addition complex containing two vinyl pyridine ligands. The dimer [RuClCO(CH3CHCN)(PPh3)(4-Vp)]2 is obtained by the reaction of [RuClCO(CH3CHCN)(PPh3)2]2 with an excess of 4-Vp. Stereochemical assignments have been made for these new complexes on the basis of IR and 1H NMR data. 相似文献
8.
The molecular and crystal structure of the nido-6-tungstadecaborane [6,6,6,6-(CO)2(PPh3)2-nido-6-WB9H13] (1) has been determined showing that the tungsten atom is incorporated into the 6-position of a nido 10-vertex (WB9) cage. The tungsten atom has a seven-coordinate capped trigonal prismatic environment and is bonded to two hydrogen and three boron atoms of the {B9H13} cage, in addition to two CO groups and two PPh3 ligands. Variable-temperature (−90°C to +50°C) 31P{1H} NMR spectroscopy of 1 reveals that the exo-polyhedral ligands about the tungsten atom are fluxional with respect to PPh3 site exchange with an activation energy (ΔG‡), at the coalescence temperature (−73°C), of <38 kJ mol−1. 相似文献
9.
The mononuclear chelated complex [RuCl(Cp)(η2-dppa)] has been synthesised and reacted with [Rh2Cl2(CO)4] to form the heterobimetallic complex [(Cp)Ru(μ-CO)2{(μ-Ph2PN(H)PPh2}RhCl2]. Complexes of [RuCl(Cp){(PPh2)2CHCH2PPh2}] have been reacted with [Rh2Cl2(CO)4] or [RhCl(CO)2(p-toluidene)]. Characterisation of these new ruthenium complexes was carried out using 31P-NMR, FAB mass spectroscopy, elemental analysis and IR spectrophotometry. 相似文献
10.
Aapo U. Hrknen Markku Ahlgrn Tapani A. Pakkanen Jouni Pursiainen 《Journal of organometallic chemistry》1997,530(1-2):191-197
Three tetranuclear clusters [Ru4H4(CO)11(PPh3)] (1), [Ru4H2(CO)12(PPh3)] (2) and [Ru3IrH(CO)12(PPh3)] (3) were formed in the reaction of [Ir(CO)Cl(PPh3)2] and Na[Ru3H(CO)11] in tetrahydrofuran. Complexes 1–3 were characterized by IR and 1H and 31P NMR, and the structure of the clusters was confirmed by single crystal X-ray analysis. In 2 and 3 one of the carbonyls bridges between two ruthenium atoms; otherwise the compounds contain only terminal carbonyls. 相似文献
11.
The product isolated from the reaction of (μ-H)2Os3(CO)9(PPh3) with ethylene is shown to be the ethylidene complex (μ-H)2Os3(CO)9(PPh3)(μ-CHCH3) (1) rather than the ethylene complex (μ-H)(H)Os3(CO)9(PPh3)(C2H4), as previously claimed. The characterization of 1 is based on a combination of 1H and 13C NMR results. The 1H NMR data (δ 6.84 (1 HD), 2.53 (3 HC), J(CD) = 7.4 Hz) establish the presence of the ethylidene moiety, whereas detailed analysis of the 1-D and 2-D 13C NMR spectra of 13CO-enriched 1 indicates the relative positions of the ethylidene, hydride, and phosphine ligands on the triosmium framework. 相似文献
12.
The dialkylamides of tin react with ironpentacarbonyl to form carbene complexes. With Me2Sn(NMe2)2 and Sn(NMe2)4 yellow dicarbene complexes are formed by addition of two Sn---N bonds to adjacent carbonyl groups. The two carbenoid systems on the central atom are parts of a chelate ligand connected by an ---O---Sn---O--- bridge. Using [Sn(NMe2)2]2, a red monomeric compound (CO)3Fe(CONMe2)2Sn containing the same cyclic structural unit can be isolated. The free activation enthalpy of rotation about the C(carbene)---N bond in the tin (IV) dicarbene complexes was found to be 16.5 kcal mol-1. 相似文献
13.
Javier A. Cabeza Angela Llamazares Víctor RieraPierrette Briard Lahcne Ouahab 《Journal of organometallic chemistry》1994,480(1-2):205-212
The compound [RU3(μ3,η2- -ampy)(μ3η1:η2-PhC=CHPh)(CO)6(PPh3)2] (1) (ampy = 2-amino-6-methylpyridinate) has been prepared by reaction of [RU3(η-H)(μ3,η2- ampy) (μ,η1:η2-PhC=CHPh)(CO)7(PPh3)] with triphenylphosphine at room temperature. However, the reaction of [RU3(μ-H)(μ3, η2 -ampy)(CO)7(PPh3)2] with diphenylacetylene requires a higher temperature (110°C) and does not give complex 1 but the phenyl derivative [RU3(μ3,η2-ampy)(μ,η 1:η2 -PhC=CHPh)(μ,-PPh2)(Ph)(CO)5(PPh3)] (2). The thermolysis of complex 1 (110°C) also gives complex 2 quantitatively. Both 1 and 2 have been characterized by0 X-ray diffraction methods. Complex 1 is a catalyst precursor for the homogeneous hydrogenation of diphenylacetylene to a mixture of cis- and trans -stilbene under mild conditions (80°C, 1 atm. of H2), although progressive deactivation of the catalytic species is observed. The dihydride [RU3(μ-H)2(μ 3,η2-ampy)(μ,η1:η2- PhC=CHPh)(CO)5(PPh3)2] (3), which has been characterized spectroscopically, is an intermediate in the catalytic hydrogenation reaction. 相似文献
14.
Sensuke Ogoshi Takuma Nishida Yoshiaki Fukunishi Ken Tsutsumi Hideo Kurosawa 《Journal of organometallic chemistry》2001,620(1-2):190-193
Isomerization of phenyl-substituted propargylplatinum(II) complex, trans-Pt(CH2CCPh)(Cl)(PPh3)2 (1) to allenyl complex, trans-Pt(CPh=C=CH2)(Cl)(PPh3)2 (2) was found to be catalyzed by zerovalent complex Pd(PPh3)4. The reaction was proposed to proceed through the transfer of the propargyl/allenyl ligand both from Pt(II) to Pd(0) and Pd(II) to Pt(0). The former transfer, which seemingly has a thermodynamic disadvantage, has unambiguously been confirmed to take place; treatment of 1 with Pd(PPh3)4 or a mixture of Pd2(dba)3 and PPh3 resulted in the formation of Pd(I) complex, Pd2(μ-PhCCCH2)(μ-Cl)(PPh3)2 which lies in equilibrium with a mixture of propargyl/allenylpalladium(II) and Pd(0) complexes. 相似文献
15.
James C. Fettinger Melvyn Rowen Churchill Karen A. Bernard Jim D. Atwood 《Journal of organometallic chemistry》1988,340(3):377-388
The adducts of O2 and SO2 with trans-MeOIr(CO)(PPh3)2 are formed in equilibria and have been characterized. Reaction of the SO2 adduct, Ir(OMe)(SO2)(CO)(PPh3)2 with dioxygen leads to the sulfato complex, Ir(Ome)(CO)(PPh3)2(SO4), the structure of which has been determined. Ir(Ome)(CO)(PPh3)2(SO4) crystallizes in the monoclinic system with a 11.958(2), b 14.163(3), c 12.231(2) Å, β 118.365(12)°, V 1822.7(6) Å3 and Z = 2. Diffraction data for 2θ = 4.5–45.0° (Mo-K) were collected with a Syntex P21 diffractometer and the structure was solved (assuming space group P21/m and an unpleasant 2-fold disordered model) and refined to R = 4.8% for all 2512 independent data (R = 3.5% for those 2042 data with ¦FO¦ > 6σ(¦F¦)). The iridium(III) atom has a distorted octahedral coordination sphere with trans PPh3 ligands and a cis-chelating bidentate O,O′-SO4 group; the structure is completed by mutually cis OMe and CO ligands. 相似文献
16.
Monika Moszner Anna M Trzeciak Józef J Zió?kowski 《Journal of molecular catalysis. A, Chemical》1998,130(3):351-248
Rhodium(II) complexes with dioximes [Rh(Hdmg)2(PPh3)]2 [I] (Hdmg=monoanion of dimethylglyoxime) and [Rh(Hdmg)(ClZndmg)(PPh3)]2 [II] catalyse hydroformylation and hydrogenation reactions of 1-hexene at 1 MPa CO/H2 and 0.5 MPa H2 at 353 K, respectively. Hydroformylation with complex [I] produces 94% of aldehydes (n/iso=2.2) and 6% 2-hexene whereas the second catalyst [II] gives ca. 40% of aldehydes (n/iso=2.1) and 60% of 2-hexene. Corresponding Rh(III) complexes are inactive in hydroformylation except of RhH(Hdmg)2(PPh3) [III], which shows activity similar to [I]. Complexes [Rh(Hdmg)2(PPh3)]2 [I], [Rh(Hdmg)(ClZndmg)(PPh3)]2 [II], RhH(Hdmg)2(PPh3) [III] and [Rh(Hdmg)2(PPh3)2]ClO4 [V] catalyse 1-hexene hydrogenation with an average TON ca. 18 cycles/mol [Rh]×min. Complex [II] has also been found to catalyse hydrogenation of cyclohexene, 1,3-cyclohexadiene and styrene. 相似文献
17.
为了观察和监测反应条件下中间产物和催化剂的变化,自行设计并安装了高温高压红外流动池。池体用不锈钢制成,窗口材料为NaCl或CaF2。它可承受100atm和200℃。整个测量系统包括高压釜、循环泵、红外池等。用Microlab-600型红外分光光度计记录图谱。池内温度和压力与反应釜桐同,可对反应液体、气体或气液混合物进行"原位"追踪。当用铑膦络合物催化剂进行丙烯氢甲酰化反应时,在近于工业反应条件下(t=10O℃,P=17atm,正丁醛溶剂),检测到催化剂母体Rh(acac)(CO)(PPh3)转化为活性物种RhH(CO)2(PPh3)2;在合成气压力较低时,只转化为RhH(CO)(PPh3)3;此活性物种随催化剂失活而消失。催化剂加氧失活后,检测到配位体三苯基膦氧化为氧化三苯基膦,催化剂生成二聚物,丙烯氧化成丙酮,追踪到原料气CO氧化为CO3的动态过程。本文对"原位"红外光谱实验方法、高温高压红外池作了介绍,并给出有关实验数据和结果。 相似文献
18.
The tail-to-tail dimerization of methyl acrylate (MA) in the presence of H2Ru(PPh3)4 (1) or H2(CO)Ru(PPh3) 3 (2) and CF3SO3H to give a mixture of linear dimers is described. In neat methyl acrylate at 85°C the reaction shows turnover numbers of 300 in 20 h and 640 in 7 d. Mechanistic studies show that the initial step of the reaction is the reduction of H2Ru(PPh3)4 (1) by MA to form Ru(MA)2 (PPh3)2 (5). After activation with CF3SO3H the catalytically active species contains only one phosphane ligand. The basic mechanistic features of the dimerization reaction have been revealed by 2H NMR spectroscopy involving the use of CF3SO3D. The deuterium-labelling studies indicate the intermediate formation of a ruthenium(II) hydride complex. Subsequent olefin insertions in this complex, followed by β-hydride elimination,lead to the linear dimeric products. 相似文献
19.
Hydrated rhodium(III) chloride reacts with azobenzene (HAzb) affording RhCl3(PhNH2)2 and the dimeric [(Azb)2RhCl]2. The latter reacts with donor ligands to give (Azb)2RhCl(L), (L=PPh3, tetrahydrofuran). With [Rh(CO)2Cl]2, azobenzene affords an unusual RhI---RhIII complex, [(Azb)2RhCl2Rh(CO)2], which can also be obtained from [Rh(CO)2Cl]2 and [(Azb)2RhCl]2. These complexes contain the ortho-metallated (phenylazo)phenyl-2C,N′ ligand, and their spectroscopic properties are summarised. 相似文献
20.
The heteronuclear metal clusters [H3MRu4(CO)12(PPh3)] and [MFe3(μ-COMe)(CO)10(PPh3)] (M = Cu, Ag or Au) have been prepared; the gold-tetraruthenium cluster has a different metal core geometry to that adopted by the copper and silver analogues, whereas all three iron-Group IB mixed-metal clusters have the same geometry. 相似文献