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1.
Rosales Merlin Castillo Jéssica González Angel González Larry Molina Karely Navarro Janeth Pacheco Inés Pérez Homero 《Transition Metal Chemistry》2004,29(2):221-228
The [OsH(CO)(NCMe)2(PPh3)2]BF4 complex (1) is an efficient and regioselective precatalyst for the hydrogenation of the nitrogen-containing ring of quinoline (Q), isoquinoline (iQ), 5,6- and 7,8-benzoquinoline (BQ), and acridine (A) under mild reaction conditions (125 °C and 4 atm H2). Kinetic studies of the hydrogenation of Q and iQ to give tetrahydroquinoline (THQ) and tetrahydroisoquinoline (THiQ), respectively, lead to the rate law r = K
1
k
2/(1 + K
1[H2])[Os][H2]2, which becomes r = K
1
k
2[Os][H2]2, at low hydrogen concentrations (below 1 atm H2); the catalytically active species is of the type [OsH(CO)(L)(
1-N)(PPh3)2]BF4 [(2a): L = NCMe, N = Q; (2b): L = N = iQ]. The generic mechanisms involve a rapid and partial hydrogenation of the coordinated substrate (N) of complex (2) to yield the corresponding dihydroderivative (DHN) species [OsH(CO)(L)(
1-DHN)(PPh3)2]BF4 [(3a): L = NCMe, DHN = DHQ; (3b): L = iQ or THiQ, DHN = DHiQ], followed by the rate-determining second hydrogenation of the DHN ligand, which yield [OsH(CO)(L)(
1-THN)(PPh3)2]BF4 [(4a): L = NCMe, THN = THQ; (4b): L = iQ or THiQ, THN = THiQ]; substitution of the THN ligand by a new molecule of the respective substrate regenerates the active species and restarts the catalytic cycle. For the hydrogenation of acridine to give 9,10-dihidroacridine (acridane), the rate law was r = k
1[Os][H2]; the mechanism involves the hydrogenation of the active species [OsH(CO)(NCMe)(
1-A)(PPh3)2]BF4
(2c) to yield acridane and the unsaturated species [OsH(CO)(NCMe)(PPh3)2]BF4 as the rate-determining step. 相似文献
2.
Merlin Rosales Ysaías Alvarado Mirixa Boves Raúl Rubio Humberto Soscún Roberto A. Sánchez-Delgado 《Transition Metal Chemistry》1995,20(3):246-251
Summary A kinetic study of the regioselective homogeneous hydrogenation of quinoline (Q) to 1,2,3,4-tetrahydroquinoline (THQ) was carried out using the cationic complex [RuH(CO)(NCMe)2(PPh3)2]BF4 (1) as the precatalyst. The experimentally determined rate law wasr = {k
2
K
1/(1+K
1[H2])}[Ru0][H2]2, which becomesr = {k
2
K
1[Ru0]–[H2]2 at low hydrogen concentrations (k
2
K
1 = 28.5M
–2 s–1 at 398 K). The corresponding activation parameters were found to be H
= 42 + 6 kJ mol–1, S
= – 115 ± 2JK–1mol–1 and G
= 92 ± 8 kJ mol–1. Complex(1) was found to react with Q in CHCl3 under reflux to yield [RuH(CO)(NCMe)(N-Q)(PPh3)2]BF4
(2) which was also isolated from the hydrogenation runs. These experimental findings, together with the results ofab initio self-consistent-field molecular orbital calculations on the free organic molecules involved, are consistent with a mechanism involving a rapid and reversible partial hydrogenation of(2) to yield the corresponding dihydroquinoline (DHQ) species [RuH(CO)(NCMe)(DHQ)(PPh3)2]BF4
(4), followed by a rate-determining second hydrogenation of DHQ to yield [RuH(CO)(NCMe)(THQ)(PPh3)2]BF4
(3). 相似文献
3.
Rosales Merlin González Ángel Mora Milagros Nader Nidal Navarro Janeth Sánchez Ligbel Soscún Humberto 《Transition Metal Chemistry》2004,29(2):205-211
Kinetic and mechanistic studies of the homogeneous hydrogenation of cyclohexanone were carried out using the cationic complexes [MH(CO)(NCMe)2(PPh3)2]BF4 (M = Ru, Os) as the catalyst precursors, which were very efficient under mild reaction conditions in 2-methoxyethanol solution. For both complexes, the catalytic hydrogenation of cyclohexanone proceeds according to the rate law r = k[M][H2]. The activation parameters were also calculated, the activation energy for the osmium catalyst being higher than for the ruthenium(I). All experimental data are consistent with a mechanism involving the oxidative addition of hydrogen as the rate-determining step of the catalytic cycle. Finally, the [MH(CO)(NCMe)2(PPh3)2]BF4 complexes were efficient precatalysts for the selective reduction of 2-cyclohexen-1-one to cyclohexanone; the reduction of the CO group of cyclohexanone only begins to take place when the ,-unsaturated ketone has been consumed. 相似文献
4.
Potential inhibitors of DNA topoisomerase II: ruthenium(II) poly-pyridyl and pyridyl-azine complexes
Manish Chandra D.S. Pandey R.P. Tripathi V.J.M. Reddy Pedro Valerga 《Journal of organometallic chemistry》2004,689(13):2256-2267
In search of new DNA probes a series of new mono and binuclear cationic complexes [RuH(CO)(PPh3)2(L)]+ and [RuH(CO)(PPh3)2(-μ-L)RuH(CO)(PPh3)2]2+ [L=pyridine-2-carbaldehyde azine (paa), p-phenylene-bis(picoline)aldimine (pbp) and p-biphenylene-bis(picoline)aldimine (bbp)] have been synthesized. The reaction products were characterized by microanalyses, spectral (IR, UV-Vis, NMR and ESMS and FAB-MS) and electrochemical studies. Structure of the representative mononuclear complex [RuH(CO)(PPh3)2(paa)]BF4 was crystallographically determined. The crystal packing in the complex [RuH(CO)(PPh3)2(paa)]BF4 is stabilized by intermolecular π-π stacking resulting into a spiral network. Topoisomerase II inhibitory activity of the complexes and a few other related complexes [RuH(CO)(PPh3)2(L)]+ {L=2,4,6-tris(2-pyridyl)-1,3,5-triazine (tptz) and 2,3-bis(2-pyridyl)-pyrazine (bppz)} have been examined against filarial parasite Setaria cervi. Absorption titration experiments provided good support for DNA interaction and binding constants have also been calculated which were found in the range 1.2 × 103-4.01 × 104 M−1. 相似文献
5.
Hydride-phosphoniodithiocarboxylate/ phosphonium-betaine isomerism in Cy3PCS2 complexes of ruthenium
《Journal of organometallic chemistry》1993,447(1):C7-C9
Reaction of Cy3PCS2 (Cy = cyclohexyl) with the hydrido complexes [RuClH(CA)(PPh3)3] (A O, S), [RuH(CO)(NCMe)2(PPh3)2]+, and [RuH(OClO3)(CO)(CNtBu)(PPh3)2] leads to the complex cations [RuH(CA)(PPh3)2(η2-S2CPCy3)]+, [Ru(η2-S2CHPCy3)(CO) (PPh3)2]+, [RuH(η1-S2CPCy3)(CO)(CNtBu)(PPh3)2]+. The σ-vinyl complex [Ru(CHCHC6H4Me-4)Cl(CO)(PPh3)2] reacts with Cy3PCS2 to give the cationic complex [Ru(CHCHC6H4Me-4) (CO)(PPh3)2(η2-S2CPCy3)]+, but this complex is not formed by hydroruthenation of HCCC6H4Me-4 by [RuH(CO)(PPh3)2(η2-S2CPCy3)]+. The inter-relationships between the above complexes are discussed. 相似文献
6.
Two pseudohalide hydride carbonyl ruthenium(II) complexes with formulae: [RuH(N3)(CO)(PPh3)3] (1) and [RuH(NCO)(CO)(PPh3)3] (2) have been synthesized by the reactions of [RuHCl(CO)(PPh3)3] with sodium azide or sodium cyanate, respectively, and are compared with the previously described thiocyanate analog [RuH(NCS)(CO)(PPh3)3]. The molecular structures of the new compounds were determined by X-ray crystallography and their spectroscopic properties have been studied. Based on the crystal structures, computational investigations have been carried out in order to determine the electronic structures of the complexes. The electronic spectra were calculated with the use of time-dependent DFT methods, and the electronic spectra of the transitions were correlated with the molecular orbitals of the complexes. 相似文献
7.
Merlin Rosales Ysaías Alvarado Nelya Gallardo Raúl Rubio 《Transition Metal Chemistry》1995,20(3):242-245
Summary Kinetic and mechanistic studies of the homogeneous hydrogenation of cyclohexane were carried out using the cationic complex [RuH(CO)(NCMe)2(PPh3)2]BF4 as the catalyst precursor, which was very efficient under mild reaction conditions in xylene solution. The experimental rate law was found to ber = {K
1
K
2
k
3/([MeCN]+K
1–(1+K
2)[C6H10]}[Ru][C6H10][H2], which became {K
2
k
3/(1 +K
2)}[Ru][H2] at high cyclohexane concentrations. The activation parameters were calculated. The kinetic data are consistent with a mechanism involving the oxidative addition of hydrogen as the rate-determining step of the catalytic cycle. 相似文献
8.
Camino Bartolomé Jose Miguel Martín-Alvarez Fernando Villafañe 《Journal of organometallic chemistry》2006,691(18):3862-3873
Halide abstraction from [Pd(μ-Cl)(Fmes)(NCMe)]2 (Fmes = 2,4,6-tris(trifluoromethyl)phenyl or nonafluoromesityl) with TlBF4 in CH2Cl2/MeCN gives [Pd(Fmes)(NCMe)3]BF4, which reacts with monodentate ligands to give the monosubstituted products trans-[Pd(Fmes)L(NCMe)2]BF4 (L = PPh3, P(o-Tol)3, 3,5-lut, 2,4-lut, 2,6-lut; lut = dimethylpyridine), the disubstituted products trans-[Pd(Fmes)(NCMe)(PPh3)2]BF4, cis-[Pd(Fmes)(3,5-lut)2(NCMe)]BF4, or the trisubstituted products [Pd(Fmes)L3]BF4 (L = CNtBu, PHPh2, 3,5-lut, 2,4-lut). Similar reactions using bidentate chelating ligands give [Pd(Fmes)(L-L)(NCMe)]BF4 (L-L = bipy, tmeda, dppe, OPPhPy2-N,N′, (OH)(CH3)CPy2-N,N′). The complexes trans-[Pd(Fmes)L2(NCMe)]BF4 (L = PPh3, tht) (tht = tetrahydrothiophene) and [Pd(Fmes)(L-L)(NCMe)]BF4 (L-L = bipy, tmeda) were obtained by halide extraction with TlBF4 in CH2Cl2/MeCN from the corresponding neutral halogeno complexes trans-[Pd(Fmes)ClL2] or [Pd(Fmes)Cl(L-L)]. The aqua complex trans-[Pd(Fmes)(OH2)(tht)2]BF4 was isolated from the corresponding acetonitrile complex. Overall, the experimental results on these substitution reactions involving bulky ligands suggest that thermodynamic and kinetic steric effects can prevail affording products or intermediates different from those expected on purely electronic considerations. Thus,water, whether added on purpose or adventitious in the solvent, frequently replaces in part other better donor ligands, suggesting that the smaller congestion with water compensates for the smaller M-OH2 bond energy. 相似文献
9.
Alan Dobson David S. Moore Stephen D. Robinson Michael B. Hursthouse Lucy New 《Polyhedron》1985,4(6):1119-1130
The hydrides [MH(O2CCF3)(CO)(PPh3)2] (M = Ru or Os) react with disubstituted acetylenes PhCCPh and PhCCMe to afford vinylic products [M{C(Ph)CHPh}(O2CCF3)(CO)(PPh3)2] and [M{C(Ph)CHMe}(O2CCF3)(CO) (PPh3)2]/[M{C(Me)CHPh}(O2CCF3)(CO)(PPh3)2] respectively. Acidolysis of these products with trifluoroacetic acid in cold ethanol liberates cis-stilbene and cis-PhHCCHMe respectively thus establishing the cis-stereochemistry of the vinylic ligands. The complexes [M(O2CCF3)2(CO)(PPh3)2] formed during the acidolysis step undergo facile alcoholysis followed by β-elimination of aldehyde to regenerate the parent hydrides [MH(O2CCF3)(CO)(PPh3)2] and thereby complete a catalytic cycle for the transfer hydrogenation of acetylenes. The molecular structure of the methanol-adduct intermediate, [Ru(O2CCF3)2(MeOH)(CO)(PPh3)2] has been determined by X-ray methods and shows that the coordinated methanol is involved in H-bonding with the monodentate trifluoroacetate ligand [MEO-H---OC(O)CF3; O...O = 2.54 Å]. The hydrides [MH(O2CCF3)(CO) (PPh3)2]react with 1,4-diphenylbutadiyne to afford the complexes [M{C(CCPh)CHPh} (O2CCF3)(CO)(PPh3)2]. The ruthenium product, which has also been obtained by treatment of [RuH(O2CCF3)(CO)(PPh3)2] with phenylacetylene, has been shown by X-ray diffraction methods to contain a 1,4-diphenylbut-1-en-3-yn-2-yl ligand. The osmium complexes [Os(O2CCF3)2(CO)(PPh3)2], [OsH(O2CCF3)(CO)(PPh3)2] and [Os{C(CCPh)CHPh}(O2CCF3)(CO)(PPh3)2] all serve as catalysts for the oligomerisation of phenylacetylene. Acetylene reacts with [Ru(O2CCF3)2(CO)(PPh3)2] in ethanol to afford the vinyl complex [Ru(CHCH2)(O2CCF3)(CO)(PPh3)2]. 相似文献
10.
Summary The rhodium(I) carbonyl compounds [Rh(CO)L22] [BF4]. 1/2CH2Clnn2 (L = PPh2 or AsPh3) react with the nucleophiles OMe−, RCOO− (R = Me, Et) under nitrogen to form [Rh(OR)(CO)L2] (1)–(2) and [Rh(OOCR)(CO)L2] (7)–(10), respectively. Addition of [Rh(CO)2(PPh3)2]-[BF 4] to OMe− under nitrogen produces [Rh(COOMe)-(CO) (PPh3)2]-MeOH (3), whilst reactions of [Rh(CO)-(PPh3)2] [BF4]·1/2CH2Cl2 and [Rh(CO)2(PPh3)2] [BF4] with OR- (R = Me, Et or n-Pr) in the presence of CO produce [Rh(COOR)(CO)2(PPh3)2] (4)–(6). The products have been characterised by i.r., 1H, 31P, 13Cn.m.r. spectroscopy and elemental analysis. 相似文献
11.
The hydride carbonyl ruthenium(II) [RuH(CO)(pyzCOO)(PPh3)2] (1), [RuH(CO)(pyz-2,3-COO[CH3])(PPh3)2]·H2O (2) and dinuclear Ru(II)/Ru(III) [RuH(CO)(PPh3)(pyz-2,3-COO)Ru(CO)Cl2(PPh3)2] (3) complexes were synthesized and characterized by IR, 1H, 31P NMR, UV-Vis spectroscopy and X-ray crystallography. The experimental studies were complemented by quantum chemical calculations, which were used to identify the nature of the interactions between the ligands and the central ion, and the orbital composition in the frontier electronic structure. Based on a molecular orbital scheme, the calculated results allowed the interpretation of the UV-Vis spectra obtained at an experimental level. The luminescence property of the complex 2 was determined. The ac magnetic susceptibility measurements showed a residual magnetism evidenced by the small values of the molar susceptibility, not exceeding 0.5 emu/mol at 2 K, a lack of a Curie-Weiss region and weak magnetic interactions below 20 K. 相似文献
12.
The reactions of [Ru(H)(Cl)(CO)(PPh3)3] with 3,5-di-tert-butyl-o-benzoquinone (dbq) and 3,4,5,6-tetrachloro-o-benzoquinone (tcq) have afforded the corresponding semiquinone complexes [RuII(dbsq)(Cl)(CO)(PPh3)2] and [RuII(tcsq)(Cl)(CO)(PPh3)2], respectively. The reaction of [Ru(H)2(CO)(PPh3)3] with tcq has furnished [RuII(tcsq)(H)(CO)(PPh3)2]. Structure determination of [Ru(dbsq)(Cl)(CO)(PPh3)2] has revealed that it is a model semiquinonoid chelate with two equal C---O lengths ( 1.291(6) and 1.296(6) Å). The complexes are one-electron paramagnetic (1.85μB) and their EPR spectra in fluid media display a triplet structure (g2.00) due to superhyperfine coupling with two trans-31P atoms (Aiso17 G). The stretching frequency of the CO ligand increases by 20 cm−1 in going from [Ru(dbsq)(Cl)(CO)(PPh3)2] to [Ru(tcsq)(Cl)(CO)(PPh3)2] consistent with electron withdrawal by chloro substituents. For the same reason the E1/2 values of the cyclic voltammetric quinone/semiquinone and semiquinone/catechol couples undergo a shift of 500 mV to higher potentials between [Ru(dbsq)(Cl)(CO)(PPh3)2] and [Ru(tcsq)(Cl)(CO)(PPh3)2]. 相似文献
13.
[RuH(CO)(SCN)(PPh3)3] and [RuH(CO){SCN}(PPh3)2(L)]{SCN} complexes (where L = benzimidazole, 2-(2-pyridyl)benzimidazole and 2,2′-bis(4,5-dimethylimidazolyl)) have been prepared and studied by IR, NMR, UV–Vis spectroscopy and X-ray crystallography. Electronic structures and bonding of the obtained complexes were defined on the basis of DFT method. Values of the ligand field parameter 10Dq and Racah’s parameters were estimated for the studied compounds, and the luminescence properties were determined. 相似文献
14.
《Journal of Coordination Chemistry》2012,65(5):407-415
The complexes [MI2(CO)3(NCMe)2] (M=Mo or W) react in CH2Cl2 at room temperature with two equivalents of 4,4'-diphenylenecarbonitrile (dpc) to afford the new seven-coordinate complexes, [MI2(CO)3(4,4'-dpc-N)2] (1 and 2) in good yield. Equimolar quantities of [MI2(CO)3(NCMe)2] and PPh3 give [MI2(CO)3(NCMe)(PPh3)], which react in situ with 4,4'-dpc to yield the mono-4,4'-diphenylenecarbonitrile complexes, [MI2(CO)3(4,4'-dpc-N)(PPh3)] (3 and 4). Treatment of the bis(alkyne) complexes, [WI2(CO)(NCMe)(η 2-RC2R)2] (R=Me and Ph) with one equivalent of 4,4'-dpc in CH2Cl2 at room temperature affords the acetonitrile displaced products, [WI2(CO)(4,4'-dpc-N)(η 2-RC2R)2] (5 and 6). Reaction of equimolar quantities of [WI2(CO)(NCMe)(η 2-PhC2Ph)2] and 2 in CH2Cl2 at room temperature gives the 4,4'-dpc-bridged complex, [WI2(CO){WI2(CO)3(4,4'-dpc-N)(4,4'-dpc- N,N')}(η 2-PhC2Ph)2] (7) in good yield. Similarly, equimolar amounts of [WI2(CO)(NCMe)(η 2-RC2R)2] (R=Me and Ph) and (4) react in CH2Cl2 to afford the bimetallic complexes, [WI2(CO){WI2(CO)(4,4'-dpc-N,N')(PPh3)}(η 2-RC2R)2] (8 and 9). The new bimetallic 4,4'-dpc-bridged alkyne complexes, [WI2(CO){WI2(CO)(4,4'-dpc-N,N')(η 2-MeC2Me)2}(η 2-MeC2Me)2] [(10), [WI2(CO){WI2(CO)(4,4'-dpc-N,N')(η 2-PhC2Ph)2}(η 2-PhC2Ph)2] (11) and [WI2(CO){WI2(CO)(4,4'-dpc-N,N')(η 2-MeC2Me)2}(η 2-PhC2Ph)2] (12) are also described. 相似文献
15.
Keith P Carruthers 《Journal of organometallic chemistry》2004,689(4):848-859
Protonation of the cycloheptatriene complex [W(CO)3(η6-C7H8)] with H[BF4] · Et2O in CH2Cl2 affords the cycloheptadienyl system [W(CO)3(η5-C7H9)][BF4] (1). Complex 1 reacts with NaI to yield [WI(CO)3(η5-C7H9)], which is a precursor to [W(CO)2(NCMe)3(η3-C7H9)][BF4], albeit in very low yield. The dicarbonyl derivatives [W(CO)2L2(η5-C7H9)]+ (L2=2PPh3, 4, or dppm, 5) were obtained, respectively, by H[BF4] · Et2O protonation of [W(CO)2(PPh3)(η6-C7H8)] in the presence of PPh3 and reaction of 1 with dppm. The X-ray crystal structure of 4 (as a 1/2 CH2Cl2 solvate) reveals that the two PPh3 ligands are mutually trans and are located beneath the central dienyl carbon and the centre of the edge bridge. The first examples of cyclooctadienyl tungsten complexes [WBr(CO)2(NCMe)2(1-3-η:5,6-C8H11)] (6) and [WBr(CO)2(NCMe)2(1-3-η:4,5-C8H11)] (7) were synthesised by reaction of [W(CO)3(NCR)3] (R=Me or Prn) with 3-Br-1,5-cod/6-Br-1,4-cod or 5-Br-1,3-cod/3-Br-1,4-cod (cod=cyclooctadiene), respectively. Complexes 6 and 7 are precursors to the pentahapto-bonded cyclooctadienyl tungsten species [W(CO)2(dppm)(1-3:5,6-η-C8H11)][BF4] and [W(CO)2(dppe)(1-5-η-C8H11)][BF4] · CH2Cl2. 相似文献
16.
[RuH(CO)(dpa)(PPh3)2]X and [RuHX(CO)(pyCHPh)(PPh3)2] (X = Cl, NCS) complexes (where dpa = 2,2′-dipyridylamine, pyCHPh = 4-(3-phenylpropyl)pyridine) have been prepared and studied using IR, NMR, UV-Vis spectroscopies and X-ray crystallography. The electronic structures and bonding of the obtained complexes were defined on the basis of the DFT method. The electronic spectra of the complexes were calculated and associated with the structure of the molecular orbitals of the complexes. The luminescence properties of the complexes were determined. 相似文献
17.
Paul K. Baker Lesley L. Howells Stuart G. Fraser Gordon W. Rogers Martin J. Snowden 《Transition Metal Chemistry》1990,15(1):71-74
Summary The seven-coordinate complexes [MI2(CO)3(NCMe)2] (M=Mo or W) react with two equivalents of L(L=py, 4Me-py, 3Cl-py or 3Br-py) or one equivalent of NN {NN=2,2-bipyridine(bipy), 1,10-phenanthroline(phen), 5,6-dimethyl-1, 10-phenanthroline (5,6-Me2-1, 10-phen), 5-Nitro-1, 10-phenanthroline (5-NO2-1, 10-phen) and C6H4(o-NH2)2 (o-diam) (for M=Mo only)} in CH2Cl2 at room temperature to give the substituted products [MI2(CO)3L2] or [MI2(CO)3(NN)] (1–17) in high yield. The compounds [MI2(CO)3(NCMe)2] react with two equivalents of NN (for M=W, NN=bipy; for M=Mo, NN=phen) to give the dicationic salts [M(CO)3(NN)2]2I(18–19). The compounds [MI2(CO)3(NCMe)2] (M=Mo or W) react with two equivalents of 5,6-Me2-1, 10-phen to yield the monocationic dicarbonyl compounds [MI(CO)2(5,6-Me2-phen)2]I (20 and21). The dicationic mixed ligand complexes [M(CO)3(bipy)(5,6-Me2-phen)]2I (22 and23) are prepared by reacting [MI2(CO)3(NCMe)2] with one equivalent of bipy, followed by anin situ reaction with 5,6-Me2-1, 10-phen to afford the products22 and23. The complexes (1–23) described in this paper have been characterised by elemental analysis (C, H and N), i.r. spectroscopy and, in selected cases,1Hn.m.r. spectroscopy. Magnetic susceptibility measurements show the compounds to be diamagnetic. 相似文献
18.
The complexes [IrH(CO)(PPh3)3], trans-[IrCI(CO)- (PPh3)2], [RhH(PPh3)4], [Pd(PPh3)4], [Pt(trans-stilbene)(PPh3)2] and [Pt(η3-CH2-COCH2)-(PPh3)2] catalyse the rearrangement of Me3SiCH2C(O)CH2Cl to CH2?C(OSiMe3)-CH2Cl. 相似文献
19.
G. Muthusamy P. Viswanathamurthi M. Muthukumar K. Natarajan 《Phosphorus, sulfur, and silicon and the related elements》2013,188(8):2115-2124
Several new hexa-coordinated ruthenium(II) and penta-coordinated rhodium(I) complexes of the types [RuCl(CO)(PPh 3 ) 2 (TSC)], [RuH(CO)(PPh 3 ) 2 (TSC)], and [Rh(PPh 3 ) 3 (TSC)] (where TSC = anion of thiosemicarbazone Schiff bases) have been prepared by the reactions of [RuHCl(CO)(PPh 3 ) 3 ], [RuH 2 (CO)(PPh 3 ) 3 )], and [RhH(PPh 3 ) 4 ] with thiosemicarbazones of 2-furaldehyde (H-FTSC), thiophene-2-carboxaldehyde (H-TCTSC), p-anisaldehyde (H-ATSC), piperonaldehyde (H-PTSC), and cyclohexanone (H-CTSC). All the new complexes obtained have been characterized on the basis of elemental analysis, IR, 1 H NMR, 31 P NMR, and electronic spectral data. 相似文献
20.
Summary
Trans-[RhCl(CO)L2] (L = PPh3, AsPh3 or PCy3) react with AgBF4 in CH2Cl2 to give the novel species [Rh-(CO)L2]+ [BF4]–.nCH2Cl2 (n = 1/2 or 1 1/2) (1–3), which we believe to be stabilised by weak solvent interaction. The corresponding stibine compound cannot be isolated by the same process, instead [Rh(CO)2(SbPh3)3]+ [BF4]– (7) is formed when the reaction is carried out in the presence of CO. When reactions designed to prepare [Rh(CO)L2]+ [BF4]– are performed in the presence of CO, or [Rh(CO)L2]+ [BF4]– complexes are reacted with CO, [Rh(CO)2L2]+ [BF4]– (L = PPh3, AsPh3 or PCy3) (4–6) are formed. If Me2CO is used as solvent in the preparation of [Rh(CO)L2]+ [BF4]– (L = PPh3 or AsPh3), then the products are the four-coordinate [Rh(CO)L2-(Me2CO)]+ [BF4]– (8,9) species. The complexes have been characterised by i.r., 31P and 1H n.m.r. spectroscopy and elemental analyses. 相似文献