共查询到20条相似文献,搜索用时 62 毫秒
1.
Almudena García-Fernández Josefina Díez Ángel Manteca Jesús Sánchez M. Pilar Gamasa Elena Lastra 《Polyhedron》2008
A series of half-sandwich ruthenium(II) complexes containing κ3(N,N,N)-hydridotris(pyrazolyl)borate (κ3(N,N,N)-Tp) and the water-soluble phosphane 1,3,5-triaza-7-phosphaadamantane (PTA) [RuX{κ3(N,N,N)-Tp}(PPh3)2−n(PTA)n] (n = 2, X = Cl (1), n = 1, X = Cl (2), I (3), NCS (4), H (5)) and [Ru{κ3(N,N,N)-Tp}(PPh3)(PTA)L][PF6] (L = NCMe (6), PTA (7)) have been synthesized. Complexes containing 1-methyl-3,5-diaza-1-azonia-7-phosphaadamantane(m-PTA) triflate [RuCl{κ3(N,N,N)-Tp}(m-PTA)2][CF3SO3]2 (8) and [RuX{κ3(N,N,N)-Tp}(PPh3)(m-PTA)][CF3SO3] (X = Cl (9), H (10)) have been obtained by treatment, respectively, of complexes 1, 2 and 5 with methyl triflate. Single crystal X-ray diffraction analysis for complexes 1, 2 and 4 have been carried out. DNA binding properties by using a mobility shift assay and antimicrobial activity of selected complexes have been evaluated. 相似文献
2.
The reactions of trans-[MoO(ONOMe)Cl2] 1 (ONOMe = methylamino-N,N-bis(2-methylene-4,6-dimethylphenolate) dianion) and trans-[MoO(ONOtBu)Cl2] 2 (ONOtBu = methylamino-N,N-bis(2-methylene-4-methyl-6-tert-butylphenolate) dianion) with PhNCO afforded new imido molybdenum complexes trans-[Mo(NPh)(ONOMe)Cl2] 3 and trans-[Mo(NPh)(ONOtBu)Cl2] 4, respectively. As analogous oxotungsten starting materials did not show similar reactivity, corresponding imido tungsten complexes were prepared by the reaction between [W(NPh)Cl4] with aminobis(phenol)s. These reactions yielded cis- and trans-isomers of dichloro complexes [W(NPh)(ONOMe)Cl2] 5 and [W(NPh)(ONOtBu)Cl2] 6, respectively. The molecular structures of 4, cis-6 and trans-6 were verified by X-ray crystallography. Organosubstituted imido tungsten(VI) complex cis-[W(NPh)(ONOtBu)Me2] 7 was prepared by the transmetallation reaction of 6 (either cis or trans isomer) with methyl magnesium iodide. 相似文献
3.
Gabriele Albertin Stefano Antoniutti Marco Bortoluzzi Gianluigi Zanardo 《Journal of organometallic chemistry》2005,690(7):1726-1738
Chloro phosphite complexes RuClTpL(PPh3) (1a, 1b) [L = P(OEt)3, PPh(OEt)2] and RuClTp[P(OEt)3]2 (1c) [Tp = hydridotris(pyrazolyl)borate] were prepared by allowing RuClTp(PPh3)2 to react with an excess of phosphite. Treatment of the chloro complexes 1 with NaBH4 in ethanol yielded the hydride RuHTpL(PPh3) (2a, 2b) and RuHTp[P(OEt)3]2 (2c) derivatives. Protonation reaction of 2 with Brønsted acids was studied and led to thermally unstable (above 10 °C) dihydrogen [Ru(η2- H2)TpL(PPh3)]+ (3a, 3b) and [Ru(η2-H2)Tp{P(OEt)3}2]+ (3c) complexes. The presence of the η2-H2 ligand is indicated by short T1 min values and JHD measurements of the partially deuterated derivatives. Aquo [RuTp(H2O)L(PPh3)]BPh4 (4), carbonyl [RuTp(CO)L(PPh3)]BPh4 (5), and nitrile [RuTp(CH3CN)L(PPh3)]BPh4 (6) derivatives [L = P(OEt)3] were prepared by substituting H2 in the η2-H2 derivatives 3. Vinylidene [RuTp{CC(H)R}L(PPh3)]BPh4 (7, 8) (R = Ph, tBu) and allenylidene [RuTp(CCCR1R2)L(PPh3)]BPh4 (9-11) complexes (R1 = R2 = Ph, R1 = Ph R2 = Me) were also prepared by allowing dihydrogen complexes 3 to react with the appropriate HCCR and HCCC(OH)R1R2 alkynes. Deprotonation of vinylidene complexes 7, 8 with NEt3 was studied and led to acetylide Ru(CCR)TpL(PPh3) (12, 13) derivatives. The trichlorostannyl Ru(SnCl3)TpL(PPh3) (14) compound was also prepared by allowing the chloro complex RuClTpL(PPh3) to react with SnCl2 · 2H2O in CH2Cl2. 相似文献
4.
Interaction of [Ru(NO)Cl3(PPh3)2] with K[N(R2PS)2] in refluxing N,N-dimethylformamide afforded trans-[Ru(NO)Cl{N(R2PS)2}2] (R = Ph (1), Pri (2)). Reaction of [Ru(NO)Cl3(PPh3)2] with K[N(Ph2PSe)2] led to formation of a mixture of trans-[Ru(NO)Cl{N(Ph2PSe)2}2] (3) and trans-[Ru(NO)Cl{N(Ph2PSe)2}{Ph2P(Se)NPPh2}] (4). Reaction of Ru(NO)Cl3 · xH2O with K[N(Ph2PO)2] afforded cis-[Ru(NO)(Cl){N(Ph2PO)2}2] (5). Treatment of [Rh(NO)Cl2(PPh3)2] with K[N(R2PQ)2] gave Rh(NO){N(R2PQ)2}2] (R = Ph, Q = S (6) or Se (7); R = Pri, Q = S (8) or Se (9)). Protonation of 8 with HBF4 led to formation of trans-[Rh(NO)Cl{HN(Pri2PS)2}2][BF4]2 (10). X-ray diffraction studies revealed that the nitrosyl ligands in 2 and 4 are linear, whereas that in 9 is bent with the Rh–N–O bond angle of 125.7(3)°. 相似文献
5.
Reactivity of the ruthenium complexes [Ru(κ3-tptz)(PPh3)Cl2] (1) and [Ru(κ3-tpy)(PPh3)Cl2] (2) [tptz = 2,4,6-tris(2-pyridyl)-1,3,5-triazine; tpy = 2,2′:6′,2″-terpyridine] with several α-amino acids [glycine (gly); leucine (leu); isoleucine (isoleu); valine (val); tyrosine (tyr); proline (pro) and phenylalanine (phe)] have been investigated. Cationic complexes with the general formulations [Ru(κ3-L)(κ2-L″)(PPh3)]+ (L = tptz or tpy; L″ = gly, leu, isoleu, val, tyr, pro, and phe] have been isolated as tetrafluoroborate salts. The resulting complexes have been thoroughly characterized by analytical, spectral and electrochemical studies. Molecular structures of the representative complexes [Ru(κ3-tptz)(val)(PPh3)]BF4 (6), [Ru(κ3-tpy)(leu)(PPh3)]BF4 (10) and [Ru(κ3-tpy)(tyr)(PPh3)]BF4 (13) have been determined crystallographically. The complexes [Ru(κ3-tptz)(leu)(PPh3)]BF4 (4), [Ru(κ3-tptz)(val)(PPh3)]BF4 (6), [Ru(κ3-tpy)(leu)(PPh3)]BF4 (10) [Ru(κ3-tpy)(tyr)(PPh3)] BF4·3H2O (13) exhibited DNA binding behavior and acted as mild Topo II inhibitors (10-40%). The complexes also inhibited heme polymerase activity of the malarial parasite Plasmodium yoelii lysate. 相似文献
6.
Prashant Kumar 《Journal of organometallic chemistry》2011,696(22):3454-3464
Reactions of the ruthenium complexes [Ru(κ3-tpy)(PPh3)Cl2], [Ru(κ3-tptz)(PPh3)Cl2] and [Ru(κ3-tpy)Cl3] [tpy = 2,2′:6′,2′′-terpyridine; tptz = 2,4,6-tris(2-pyridyl)-1,3,5-triazine] with diphenyl-(2-pyridyl)-phosphine (PPh2Py) have been investigated. The complexes [Ru(κ3-tpy)(PPh3)Cl2] and [Ru(κ3-tptz)(PPh3)Cl2] reacted with PPh2Py to afford [Ru(κ3-tpy)(κ1-P-PPh2Py)2Cl]+ (1) and [Ru(κ3-tptz)(κ1-P-PPh2Py)2Cl]+ (2), which were isolated as their tetrafluoroborate salts. Under analogous conditions, [Ru(κ3-tpy)Cl3] gave a neutral complex [Ru(κ3-tpy)(κ1-PPh2Py)Cl2] (3). Upon treatment with an excess of NH4PF6 in methanol, 1 and 2 gave [Ru(κ3-tpy)(κ1-P-PPh2Py)(κ2-P,N-PPh2Py)](PF6)2 (4) and [Ru(κ3-tptz)(κ1-P-PPh2Py)(κ2-P,N-PPh2Py)](PF6)2 (5) containing both monodentate and chelated PPh2Py. Further, 4 and 5 reacted with an excess of NaCN and CH3CN to afford [Ru(κ3-tpy)(κ1-P-PPh2Py)2(CN)](PF6) (6), [Ru(κ3-tpy)(κ1-P-PPh2Py)2(NCCH3)](PF6)2 (7), [Ru(κ3-tptz)(κ1-P-PPh2Py)2(CN)]PF6 (8) and [Ru(κ3-tptz)(κ1-P-PPh2Py)2(NCCH3)](PF6)2 (9) supporting hemi labile nature of the coordinated PPh2Py. The complexes have been characterized by elemental analyses, spectral (IR, NMR, electronic absorption, FAB-MS), electrochemical studies and structures of 1, 2 and 3 determined by X-ray single crystal analyses. At higher concentration level (40 μM) the complexes under investigation exhibit inhibitory activity against DNA-Topo II of the filarial parasite S. cervi and 3 catalyses rearrangement of aldoximes to amide under aerobic conditions. 相似文献
7.
R. Lalrempuia Patrick J. Carroll K.A. Kreisel 《Journal of organometallic chemistry》2005,690(17):3990-3996
The reactions of [(ind)Ru(PPh3)2CN] (ind = η5-C9H7) (1) and [CpRu(PPh3)2CN] (Cp = η5-C5H5) (2) with [(η6-p-cymene)Ru(bipy)Cl]Cl (bipy = 2,2′-bipyridine) (3) in the presence of AgNO3/NH4BF4 in methanol, respectively, yielded dicationic cyano-bridged complexes of the type [(ind)(PPh3)2Ru(μ-CN)Ru(bipy)(η6-p-cymene)](BF4)2 (4) and [Cp(PPh3)2Ru(μ-CN)Ru(bipy)(η6-p-cymene)](BF4)2 (5). The reaction of [CpRu(PPh3)2CN] (2), [CpOs(PPh3)2CN] (6) and [CpRu(dppe)CN] (7) with the corresponding halide complexes and [(η6-p-cymene)RuCl2]2 formed the monocationic cyano-bridge complexes [Cp(PPh3)2Ru(μ-CN)Os(PPh3)2Cp](BF4) (8), [Cp(PPh3)2Os(μ- CN)Ru(PPh3)2Cp](BF4) (9) and [Cp(dppe)Ru(μ-CN)Os(PPh3)2Cp](BF4) (10) along with the neutral complexes [Cp(PPh3)2Ru(μ-CN)Ru (η6-p-cymene)Cl2] (11), [Cp(PPh3)2Os(μ-CN)Ru(η6-p-cymene)Cl2] (12), and [Cp(dppe) Ru(μ-CN)Ru(η6-p-cymene)Cl2] (13). These complexes were characterized by FT IR, 1H NMR, 31P{1H} NMR spectroscopy and the molecular structures of complexes 4, 8 and 11 were solved by X-ray diffraction studies. 相似文献
8.
Stefan Buck 《Journal of organometallic chemistry》2006,691(12):2774-2784
The dinuclear ruthenium complexes [Ru2(μ-sac)2(CO)6] (1), [Ru2(μ-sac)2(CH3CN)2(CO)4] (3), [Ru2(μ-sac)2(CO)5(PPh3)] (4) and [Ru2(μ-sac)2(CO)4(PPh3)2] (5) as well as the tetranuclear ruthenium complex [Ru2(μ-sac)2(CO)5]2 (2) (sac = saccharinate, C7H4NO3S−) were synthesized starting from Ru3(CO)12 and saccharin. X-ray crystal structure analysis of 1, 3A × p-xylene, 4 × CH2Cl2 and 5 × 3CH2Cl2 showed that the core is bridged through the amidate moieties of the two saccharinate ligands, with a head-tail arrangement in complexes 1, 3A and 5, and a head-head arrangement in 4. For complex 3, an equilibrium mixture of the head-head regioisomer 3A and a second species 3b exists in solution. Complexes 1 and 2 are suitable catalysts for the cyclopropanation of nucleophilic alkenes (styrene, cyclohexene and 2-methyl-2-butene) with methyl diazoacetate. 相似文献
9.
Treatment of either RuHCl(CO)(PPh3)3 or MPhCl(CO)(PPh3)2 with HSiMeCl2 produces the five-coordinate dichloro(methyl)silyl complexes, M(SiMeCl2)Cl(CO)(PPh3)2 (1a, M = Ru; 1b, M = Os). 1a and 1b react readily with hydroxide ions and with ethanol to give M(SiMe[OH]2)Cl(CO)(PPh3)2 (2a, M = Ru; 2b, M = Os) and M(SiMe[OEt]2)Cl(CO)(PPh3)2 (3a, M = Ru; 3b, M = Os), respectively. 3b adds CO to form the six-coordinate complex, Os(SiMe[OEt]2)Cl(CO)2(PPh3)2 (4b) and crystal structure determinations of 3b and 4b reveal very different Os-Si distances in the five-coordinate complex (2.3196(11) Å) and in the six-coordinate complex (2.4901(8) Å). Reaction between 1a and 1b and 8-aminoquinoline results in displacement of a triphenylphosphine ligand and formation of the six-coordinate chelate complexes M(SiMeCl2)Cl(CO)(PPh3)(κ2(N,N)-NC9H6NH2-8) (5a, M = Ru; 5b, M = Os), respectively. Crystal structure determination of 5a reveals that the amino function of the chelating 8-aminoquinoline ligand is located adjacent to the reactive Si-Cl bonds of the dichloro(methyl)silyl ligand but no reaction between these functions is observed. However, 5a and 5b react readily with ethanol to give ultimately M(SiMe[OEt]2)Cl(CO)(PPh3)(κ2(N,N-NC9H6NH2-8) (6a, M = Ru; 6b, M = Os). In the case of ruthenium only, the intermediate ethanolysis product Ru(SiMeCl[OEt])Cl(CO)(PPh3)(κ2(N,N-NC9H6NH2-8) (6c) was also isolated. The crystal structure of 6c was determined. Reaction between 1b and excess 2-aminopyridine results in condensation between the Si-Cl bonds and the N-H bonds with formation of a novel tridentate “NSiN” ligand in the complex Os(κ3(Si,N,N)-SiMe[NH(2-C5H4N)]2)Cl(CO)(PPh3) (7b). Crystal structure determination of 7b shows that the “NSiN” ligand coordinates to osmium with a “facial” arrangement and with chloride trans to the silyl ligand. 相似文献
10.
Susie Douglas Mary F. Mahon Michael K. Whittlesey 《Journal of organometallic chemistry》2005,690(23):5027-5035
Addition of excesses of N-heterocyclic carbenes (NHCs) IEt2Me2, IiPr2Me2 or ICy (IEt2Me2 = 1,3-diethyl-4,5-dimethylimidazol-2-ylidene; IiPr2Me2 = 1,3-diisopropyl-4,5-dimethylimidazol-2-ylidene; ICy = 1,3-dicyclohexylimidazol-2-ylidene) to [HRh(PPh3)4] (1) affords an isomeric mixture of [HRh(NHC)(PPh3)2] (NHC = IEt2Me2 (cis-/trans-2), IiPr2Me2 (cis-/trans-3), ICy (cis-/trans-4) and [HRh(NHC)2(PPh3)] (IEt2Me2(cis-/trans-5), IiPr2Me2 (cis-/trans-6), ICy (cis-/trans-7)). Thermolysis of 1 with the aryl substituted NHC, 1,3-dimesityl-4,5-dihydroimidazol-2-ylidene (IMesH2), affords the bridging hydrido phosphido dimer, [{(PPh3)2Rh}2(μ-H)(μ-PPh2)] (8), which is also the reaction product formed in the absence of carbene. When the rhodium precursor was changed from 1 to [HRh(CO)(PPh3)3] (9) and treated with either IMes (=1,3-dimesitylimidazol-2-ylidene) or ICy, the bis-NHC complexes trans-[HRh(CO)(IMes)2] (10) and trans-[HRh(CO)(ICy)2] (11) were formed. In contrast, the reaction of 9 with IiPr2Me2 gave [HRh(CO)(IiPr2Me2)2] (cis-/trans-12) and the unusual unsymmetrical dimer, [(PPh3)2Rh(μ-CO)2Rh(IiPr2Me2)2] (13). The complexes trans-3, 8, 10 and 13 have been structurally characterised. 相似文献
11.
《Journal of organometallic chemistry》2005,690(8):1947-1958
The complexes [ReCl2{N2C(O)Ph}(Hpz)(PPh3)2] (1) (Hpz = pyrazole), [ReCl2{N2C(O)Ph}(Hpz)2(PPh3)] (2), [ReCl2(HCpz3)(PPh3)][BF4] (3) and [ReCl2(3,5-Me2Hpz)3(PPh3)]Cl (4) were obtained by treatment of the chelate [ReCl2{η2-N,O-N2C(O)Ph}(PPh3)2] (0) with hydrotris(1-pyrazolyl)methane HCpz3 (1,3), pyrazole Hpz (1,2), hydrotris(3,5-dimethyl-1-pyrazolyl)methane HC(3,5-Me2pz)3 (4) or dimethylpyrazole 3,5-Me2Hpz (4). Rupture of a C(sp3)-N bond in HCpz3 or HC(3,5-Me2pz)3, promoted by the Re centre, has occurred in the formation of 1 or 4, respectively. All compounds have been characterized by elemental analyses, IR and NMR spectroscopy, FAB-MS spectrometry, cyclic voltammetry and, for 1 · CH2Cl2 and 3, also by single crystal X-ray analysis. The electrochemical EL Lever parameter has been estimated, for the first time, for the HCpz3 and the benzoyldiazenide NNC(O)Ph ligands. 相似文献
12.
Mohammad El-khateeb Khawla Damer Wolfgang Weigand 《Journal of organometallic chemistry》2007,692(11):2227-2233
A series of mononuclear ruthenium complexes containing pyridine- and pyrimidine-2-thiolato ligands was prepared and characterized. The new compounds of general formula CpRu(PPh3)(κ2S,N-SR) (1) (SR = pyridine-2-thiolate (a), pyrimidine-2-thiolate (b)) were prepared directly by reacting the thiolato anions (RS−) with CpRu(PPh3)2Cl. Complexes 1 readily react with NOBF4 or CO in THF at room temperature to give [CpRu(PPh3)(NO)(κ1S-HSR)][BF4]2 (2) and CpRu(PPh3)(CO)(κ1S-SR) (3), respectively. The one-pot reaction of CpRu(PPh3)2Cl, thiolato anions and bis(diphenylphosphino)ethane (dppe) gave CpRu(dppe)(κ1S-SR) [dppe: Ph2PCH2CH2PPh2 (4)]. The complex salts, [CpRu(PPh3)2(κ1S-HSR)]BPh4 (5) are prepared by mixing CpRu(PPh3)2Cl, HSR and NaBPh4 at room temperature. The structures of CpRu(PPh3)(κ2S,N-Spy) (1a), [CpRu(PPh3)(NO)(κ1S-HSpy)][BF4]2 (2a) and CpRu(PPh3)(CO)(κ1S-Spy) (3a), (py = C5H4N) have been determined. 相似文献
13.
Chi-Tung Yeung Wing-Sze Lee Chui-Shan Tsang Shek-Man Yiu Wing-Tak Wong Wai-Yeung Wong Hoi-Lun Kwong 《Polyhedron》2010
Three new optically pure C1-terpyridine ligands (L1–3) were prepared and the copper(II) complexes, of formula [Cu(L)Cl2], the rhodium(III) complexes, of formula [Rh(L)Cl3], and the ruthenium(II) complexes, of formula cis- or trans-[Ru(L)(X)Cl2] (X = DMSO or CO), were synthesized. Structures of a chiral C1-ligand, a copper complex, a rhodium complex and a ruthenium DMSO complex were analysed using X-ray crystal structure analysis. The copper, rhodium and ruthenium complexes were shown to be precursors of catalysts for cyclopropanation. Reaction of [Cu(L)Cl2], [Rh(L)Cl3] or cis- or trans-[Ru(L)(X)Cl2] with AgOTf converted the complex to catalyst, which in the case of trans-[Ru(L)(CO)Cl2] gave enantioselectivities of up to 67% ee for the cis-isomers of styrene cyclopropanes with t-butyl diazoacetate. Comparisons with C2-analog of copper, rhodium and ruthenium catalysts were made. 相似文献
14.
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
15.
The neutral, octahedral ruthenium vinylidene complexes mer,trans-[(PNN)Cl2Ru(CCHR)] (PNN = N-(2-diphenylphosphinobenzylidene)-2-(2-pyridyl)ethylamine; R = Ph, 1a; R = tBu, 1b) are reported. An X-ray crystallographic study of 1a confirms the tridentate, meridional coordination mode of the PNN ligand. Compounds 1a and 1b undergo regioselective electrophilic addition with HBF4 · Et2O at Cβ of the vinylidene ligand at low temperatures, and are cleanly and quantitatively converted to the ruthenium carbynes mer,trans-[(PNN)Cl2Ru(CCH2R)][BF4] (R = Ph, 2a; R = tBu, 2b). Carbynes 2a and 2b are stable only at low temperatures (<−50 °C). Complex 1a undergoes ligand substitution with L to yield mer,trans-[(PNN)Cl2Ru(L)] (L = MeCN, 3a; L = CO, 3b). 相似文献
16.
Anna Louisa Noffke Wim Wätjen Bernhard Spingler Peter C. Kunz 《Journal of organometallic chemistry》2011,696(5):1096-10800
The tetranuclear ruthenium arene compound [(cym)4Ru4(2)Cl6]Cl2 (3) (cym = η6-p-cymene, 2 = 1,2-bis(di-N-methylimidazol-2-ylphosphino)ethane) was prepared and characterised by one- and two-dimensional NMR techniques. Its cytotoxicity against four different cell lines was determined and, with an approximate IC50 of >100 μM 3 can be regarded as non-toxic. Its partition coefficient in n-octanol/water (log D7.4) was also determined. The structures of complex 3 as well as of the related compound [(cym)2Ru2(4)Cl2]Cl2 (5) (4 = 1,2-bis(di-N-methylimidazol-2-ylphosphino)ethane dioxide) were determined by single crystal structure analysis. Upon oxidation in protic solvents, ligand 2 shows P-C bond cleavage reactions to yield P,P′-bis(N-methylimidazol-2-yl)ethylene diphosphinic acid (6). 相似文献
17.
Matthew Daniels 《Journal of organometallic chemistry》2007,692(8):1716-1725
Exchange of PMe2Ph for PPh3 in (η5-pentadienyl)ruthenium{bis(triphenylphosphine)}chloride, (η5-C5H7)Ru(PPh3)2Cl (1) under first order conditions proceeds rapidly in THF at room temperature. A pseudo-first order rate constant of 17 ± 2 × 10−4 s−1 is obtained for the reaction at 21 °C. The rate constant is essentially independent of the phosphine concentration. The activation parameters, ΔH† = 16.1 ± 0.4 kcal mol−1 and ΔS† = −16 ± 1 cal K−1 mol−1 differ from those reported for phosphine exchange in CpRu(PPh3)2Cl (2) and (η5-indenyl)Ru(PPh3)2Cl (3). The reaction of 1 with PMe2Ph is about 70 times faster than the reaction of 2 at 30 °C and some 40 times faster than the reaction of 3 at 20 °C. (η5-C5H7)Ru(PPh3)2Cl(1) is more active than the ruthenium(II) complexes 2, 3, and TpRu(PPh3)2Cl (4) in the catalytic dimerization of terminal alkynes with nearly quantitative conversion of PhCCH and FcCCH at ambient temperature in 24 h. The enhanced substitution rate is accompanied by >50% conversion of phenylacetylene to oligomeric products. Reaction of 1 with NaPF6 in acetonitrile yields the cationic ruthenium(II) complex [(η5-C5H7)Ru(PPh3)2(CH3CN)][PF6] (7). The latter complex is much less active in reactions with phenylacetylene than 1 but avoids the formation of oligomeric products. 相似文献
18.
Reaction of the bis-bidentate ligand, 1,3-bis((3-(pyridin-2-yl)-1H-pyrazol-1-yl)methyl)benzene (NN∩NN), containing two chelating pyrazolyl-pyridine units connected by an aromatic spacer with platinum group metal complexes results in a series of cationic binuclear complexes, [(η6-arene)2Ru2(NN∩NN)Cl2]2+ (arene = C6H6, 1; p-iPrC6H4Me, 2; C6Me6, 3), [(η5-C5Me5)2M2(NN∩NN)Cl2]2+ (M = Rh, 4; Ir, 5), [(η5-C5H5)2M2(NN∩NN)(PPh3)2]2+ (M = Ru, 6; Os, 7), [(η5-C5Me5)2Ru2(NN∩NN)(PPh3)2]2+ (8) and [(η5-C9H7)2Ru2(NN∩NN)(PPh3)2]2+ (9). All these complexes have been isolated as their hexafluorophosphate salts and fully characterized by use of a combination of NMR spectroscopy, IR spectroscopy and mass spectrometry. The solid state structures of three complexes, [2][PF6]2, [4][PF6]2 and [6][PF6]2, has been determined by X-ray crystallographic studies. 相似文献
19.
Pradipta Kumar Basu Concepción López Mercè Font-Bardía 《Journal of organometallic chemistry》2009,694(22):3633-441
The syntheses and characterization of two novel ferrocene derivatives containing 3,5-diphenylpyrazole units of general formula [1-R-3,5-Ph2-(C3N2)-CH2-Fc] {Fc = (η5-C5H5)Fe(η5-C5H4) and R = H (2) or Me (3)} together with a study of their reactivity with palladium(II) and platinum(II) salts or complexes under different experimental conditions is described. These studies have allowed us to isolate and characterize trans-[Pd{1-Me-3,5-Ph2-(C3N2)-CH2-Fc]}2Cl2] (4a) and three different types of heterodimetallic complexes: cis-[M{1-Me-3,5-Ph2-(C3N2)-CH2-Fc]}Cl2(dmso)] {M = Pd (5a) or Pt (5b)}, the cyclometallated products [M{κ2-C,N-[3-(C6H4)-1-Me-5-Ph-(C3N2)]-CH2-Fc}Cl(L)] with L = PPh3 and M = Pd (6a) or Pt (6b) or L = dmso and M = Pt (8b) and the trans-isomer of [Pt{1-Me-3,5-Ph2-(C3N2)-CH2-Fc]}Cl2(dmso)] (7b). In compounds 4a, 5a, 5b and 7b, the ligand behaves as a neutral N-donor group; while in 6a, 6b and 8b it acts as a bidentate [C(sp2,phenyl),N(pyrazole)]− group. A comparative study of the spectroscopic properties of the compounds, based on NMR, IR and UV-Visible experiments, is also reported. 相似文献
20.
The triple ligand transfer reaction between planar-chiral cyclopentadienyl-ruthenium complexes [Cp′Ru(NCMe)3][PF6] (1) (Cp′ = 1-(COOR2)-2-Me-4-R1C5H2; R1 = Me, Ph, t-Bu) and iron complexes CpFe(CO)(L)X (2) (L = PMe3, PMe2Ph, PMePh2, PPh3; X = I, Br) resulted in the formation of metal-centered chiral ruthenium complexes Cp′Ru(CO)(L)X (3) in moderate yields with diastereoselectivities of up to 68% de. The configurations of some major diastereomers were determined to be by X-ray crystallography. The diastereoselectivity of 3 was under kinetic control and not affected by the steric effect of the substituents on the Cp′ ring of 1 and the phosphine of 2. Although the double ligand transfer reaction between [Cp′Ru{P(OMe)3}(NCMe)2][PF6] (7) and CpFe(CO)2X (8) produced Cp′Ru{P(OMe)3}(CO)X (9), the selectivity at the ruthenium center was low. 相似文献