共查询到20条相似文献,搜索用时 12 毫秒
1.
Michael MuehlhoferThomas Strassner Eberhardt HerdtweckWolfgang A Herrmann 《Journal of organometallic chemistry》2002,660(2):121-126
Novel bridged platinum(II) biscarbene complexes are reported: 1,1′-dimethyl-3,3′-methylene-4-diimidazolin-2,2′-diylidene platinum(II) (3) and 1,1′-dimethyl-3,3′-ethylene-4-diimidazolin-2,2′-diylidene platinum(II) complexes 4 are directly accessible in high yields starting from platinum halides. The one-pot synthesis obviates the need for multi-step reactions via metal precursors or free carbenes. An X-ray crystal structure of 1,1′-dimethyl-3,3′-methylene-4-diimidazolin-2,2′-diylidene platinum(II) dibromide (3b) confirmed the structural similarity to the known corresponding palladium complexes. Since free 1,1′-di-R-3,3′-methylene-4-diimidazolin-2,2′-diylidenes are only available in low yields this synthetic route provides an easy access to the corresponding carbene complexes. 相似文献
2.
Murugesan Velayudham Subramanian Singaravadivel Seenivasan Rajagopal Perumal Ramamurthy 《Journal of organometallic chemistry》2009,694(25):4076-4083
Six new homobimetallic and heterobimetallic complexes of rhenium(I) and ruthenium(II) bridged by ethynylene spacer [(CO)3(bpy)Re(BL)Re(bpy)(CO)3]2+ [Cl(bpy)2Ru(BL)Ru(bpy)2Cl]2+ and [(CO)3(bpy)Re(BL)Ru(bpy)2Cl]2+ (bpy = 2,2′-bipyridine, BL = 1,2-bis(4-pyridyl)acetylene (bpa) and 1,4-bis(4-pyridyl)butadiyne (bpb) are synthesized and characterized. The electrochemical and photophysical properties of all the complexes show a weak interaction between two metal centers in heterobimetallic complexes. The excited state lifetime of the complexes is increased upon introduction of ethynylene spacer and the transient spectra show that this is due to delocalization of electron in the bridging ligand. Also, intramolecular energy transfer from *Re(I) to Ru(II) in Re–Ru heterobimetallic complexes occurs with a rate constant 4 × 107 s−1. 相似文献
3.
Ronald Lindner Goran N. Kaluđerović Reinhard Paschke Christoph Wagner Dirk Steinborn 《Polyhedron》2008
Reactions of [PtMe3(OCMe2)3](BF4) and [(PtMe3I)4] with pyrazole (pzH) afforded mononuclear pyrazole platinum(IV) complexes [PtMe3(pzH)3](BF4) (1) and [PtMe3I(pzH)2] (2), respectively. The formation of dinuclear pyrazolato bridged platinum(IV) complexes (PPN)[(PtMe3)2(μ-pz)3] (3), (PPN)[(PtMe3)2(μ-I)(μ-pz)2] · 1/2Et2O (4) and [K(18C6)][(PtMe3)2(μ-I)(μ-pz)2] (5) was achieved by the reaction of each 1 and 2 with [PtMe3(OCMe2)3](BF4) in the presence of KOAc followed by reaction with (PPN)Cl (PPN+ = bis(triphenylphosphine)iminium cation) and 18C6, respectively. The reaction of complex 4 with AgO2CCF3 followed by addition of RSR′ (R/R′ = Me/Me, Me/Ph) resulted in the formation of complexes [(PtMe3)2(μ-pz)2(μ-RSR′)] (R/R′ = Me/Me, 6; Me/Ph, 7). All complexes were characterized unambiguously by microanalysis and NMR (1H, 13C) spectroscopic investigations. Additionally, crystal structures of complexes 3 and 4 as well as DFT calculation are presented. Furthermore, in vitro studies on the anti-proliferative activity of complexes 2 and 5 were carried out. 相似文献
4.
I. Ara J. R. Berenguer J. Fornis E. Lalinde M. T. Moreno 《Journal of organometallic chemistry》1996,510(1-2):63-70
The dialkynyl complexes cis-[Pt(C CR)2L2] [R = Ph, L2 = 2PPh3, 2PEt3, dppe (dppe = 1,2-bis(diphenylphosphino)ethane]; R ---tBu, L2 = 2PPh3, dppe) react with silver perchlorate in a molar ratio 1:0.5 to give platinum-silver perchlorate salts of the type [Pt2 Ag(C CR)4L4](ClO4) in excellent yield. The X-ray crystal structure of [Pt2Ag(C = CPh)4(PPh3)4](ClO4) 1 shows that the cation is formed by two nearly orthogonal cis-[Pt(C CPh)2(PPh3)2] units connected through a silver cation which is unsymmetrically π-bonded to all four acetylene fragments. Similar reactions of cis-[Pt(C CR)2L2] with one equivalent of AgClO4 afford cationic complexes of general formula [PtAg(C CR)2L2](ClO4), which are believed to be salts, [Pt2Ag2(C CR)4L4](ClO4)2. 相似文献
5.
Chi-He Chen Jyun-Siang Peng Ming Chen Hsin-Ying Lu Chia-Jung Tsai Chao-Sen Yang 《Colloid and polymer science》2010,288(7):731-738
High molecular weight poly(butylene succinate) (PBSu), poly(propylene succinate), and PBSu-rich copolyesters were synthesized
using an effective catalyst, titanium tetraisopropoxide. The compositions of the copolyesters were determined in three ways
from 1H and 13C NMR spectra, and good agreement between the results was obtained. The analysis of the carbonyl carbon spectra indicates
a random distribution of the comonomers. Thermal properties were studied using a differential scanning calorimeter and a thermogravimetric
analyzer. No significant difference exists among the thermal stabilities of these polyesters. However, the window between
the glass transition and the melting temperatures becomes narrower with the increase in the concentration of propylene succinate
in the copolymers. Additionally, the cold crystallization ability reduces considerably. Wide-angle X-ray diffractograms of
isothermally crystallized copolyesters also follow the same trend. 相似文献
6.
Martin J. Brown 《Journal of organometallic chemistry》2004,689(18):2872-2879
The dimeric ferrocenyl-selenolate complexes of Pd and Pt, [{μ-η1-Fe(η5-C5H4Se)2}M(PnBu3)]2 (M = Pd 2, Pt 3), and the monomeric ferrocenyl(bis-selenolate) complex of platinum, [{η2-Fe(C5H4Se)2}Pt(PnBu3)2] (4), have been prepared from 1,1′-bis(trimethylsilylseleno)ferrocene 1 and trans-MCl2(PnBu3)2 and cis-PtCl2(PnBu3)2, respectively. Complexes 2 and 3 contain two edge-sharing, square-planar metal centres forming a planar M2Se2 four-membered ring and exhibit two one-electron redox waves indicating electronic communication between the two Fe centers. 相似文献
7.
Three new binudear cobalt (II) complexes with extended te-tracarboxylato- bridge have been synthesized and characterized, namely [Co2 (PMTA) (bpy)4] (1), [Co2(PMTA)-(phen)4] (2) and [Co2(PMTA) (NO2phen)4] (3), where PMTA represents the tetraanion of pyroniellitic acid, and bpy, phen, NO2-phen denote 2,2'-bipyridine, 1,10-phenan-throline; 5-nirto-1, 10-plienanthroline, respectively. Based on elemental analyses, molar conductivity measurements, IR and electronic spectra studies, it is proposed that these complexes have PMTA-bridged structures and consist of two cobalt (II) ions, each in a distorted octahedral environment. These complexes were further characterized by variable temperature magnetic susceptibility measurements (4-300 K) and the observed data were successfully simulated by the equation based on the spin Hamiltonian operator, giving the exchange integral J = - 1.02 cm-1 for 1, J = -1.21 cm-1 for 2 and J = - 1.18 cm-1 for 3, respectively. These results revealed the operation of antiferromagneti 相似文献
8.
The carbene-ligand precursors methylenebis(N-alkylimidazolium) iodide (alkyl = methyl, neo-pentyl) and ethylenebis(N-methylimidazolium) chloride have been used in the preparation of several new Ru(II)-p-cymene complexes where the ligand behaves as mono- and bidentate. The molecular structures of the two biscarbene-complexes are reported. From the data reported, we can conclude that steric reasons (mainly the bisimidazolium linkers, methylene/ethylene) are the main factors determining both reactivity and synthetic difficulties of the products reported. 相似文献
9.
Summary Two binuclear AgI complexes, [{Ag(dppp)}2](NO3)2 (1) and [{Ag(dppb)}2(NO3)]2 (2) (dppp = Ph2P(CH2)3PPh2, dppb = Ph2P(CH2)4PPh2], were synthesized and characterized by elemental analysis, t.g., i.r. and 31P-n.m.r. spectra. Single crystals of complex (2) were obtained from MeOH-CHCl3. The X-ray crystal structure shows that the dppb ligand is bidentate, with two ligands bridging two metal ions to form a centrosymmetric dimer. 相似文献
10.
Yang Ruina Lin Kunhua Hou Yimin Wang Dongmei Jin Douman Luo Baosheng Chen Liaorong 《Transition Metal Chemistry》1997,22(3):254-258
Binuclear copper(I) complexes [Cu(dppm)(NO3)]2 (1), dppm=Ph2PCH2PPh2, [Cu(dppm)(2,9-Me2Phen)]2(NO3)2 (2), [Cu(dppm)(I)]2 (3) and [Cu(dppm)(py)]2(NO3)2 (4), (py=pyridine) have been synthesized by ligand reduction of cupric nitrate with dppm in EtOH and characterized by elemental analyses, molecular weight determination, t.g.a., 31P-n.m.r spectra; their electronic conductivities and c.v. waves have also been measured. The results show that dppm coordinates as a bridging bidentate ligand to the CuI atoms, and that NO3 behaves as a monodentate ligand or free ion in the newly prepared complexes. 相似文献
11.
Gigler P Bechlars B Herrmann WA Kühn FE 《Journal of the American Chemical Society》2011,133(5):1589-1596
A detailed study investigating the mechanism of the hydrosilylation of 4-F-acetophenone by N-heterocyclic biscarbene rhodium(I) complexes was performed, delivering substantial experimental evidence for a recently proposed catalytic cycle and explaining the observed side-product formation. Labeling experiments, silylene trapping reactions, and specific catalytic reactions were employed to substantiate each step of the catalytic cycle and explain the differences observed for different types of chiral catalysts. It is further shown that hydrosilylation and dehydrocoupling reactions with dihydrosilanes are mechanistically related. 相似文献
12.
Mairéad E. Kelly Santiago Gómez-Ruiz Dirk Steinborn Christoph Wagner Harry Schmidt 《Transition Metal Chemistry》2008,33(6):721-727
The preparation of platinum(II) complexes of the types [PtCl2{Y(CH2CH2O)
x
CH2CH2Y}] (Y: imidazol-1-yl, im; pyrazol-1-yl, pz or benzimidazol-1-yl, bim) and [PtI2{im(CH2CH2O)
x
CH2CH2im}] with varying ligand backbone length (x between 0 and 3) is described. A new bis(pyrazol-1-yl) polyether compound, pz(CH2CH2O)2CH2CH2pz, is reported. Spectroscopic characterization of the complexes is discussed. Two crystal structures of the general formula
[PtCl2{im(CH2CH2O)
x
CH2CH2im}] (x is 1 or 3) are also reported. 相似文献
13.
Carbene complexes of chromium and tungsten with a bridging furan substituent were synthesized from lithiated furan precursors and metal hexacarbonyls. The binuclear biscarbene complexes [(CO)5M{C(OEt)-C4H2O-C(OEt)}M'(CO)5](M = M'= Cr (3), W (4)) were obtained as well as the corresponding monocarbene complexes [M{C(OEt)-C(4)H3O}(CO)5](M = Cr (1), W (2)). A method of protecting the carbene moiety during the metal acylate stage was used to increase not only the yields of the binuclear Fischer biscarbene complexes 3 and 4 but to establish a method to synthesize analogous mixed heterobinuclear carbene complexes (M = W, M'= Cr (5)) in high yields. The binuclear biscarbene complexes 3 and 5 were reacted with 3-hexyne and yielded the corresponding benzannulated monocarbene complexes [M{C(OEt)-C14H17O3}(CO)5](M = Cr (6), W(7)). Complex 5 reacted regioselectively with the benzannulation reaction occurring at the chromium-carbene centre. The major products from refluxing 3 in the presence of [Pd(PPh3)4] were a monocarbene-ester complex [Cr{C(OEt)-C4H2O-C(O)OEt}(CO)5](8), the 2,5-diester of furan (9) and a carbene-carbene coupled olefin EtOC(O)-C4H2O-C(OEt)=C(OEt)-C4H2O-C(O)OEt (10). X-Ray structure analysis of 4 and 6 confirmed the molecular structures of the compounds in the solid state and aspects of electron conjugation between the transition metals and the furan substituents in the carbene ligands were investigated. 相似文献
14.
Gary Belchem Jonathan W. Steed Derek A. Tocher 《Journal of organometallic chemistry》1993,460(2):C30-C33
Reaction of the ruthenium(IV) chloro-bridged dimer [{Ru(η3 : η3-C10H16)Cl(μ-Cl)}2], 1, with ethanethiol (EtSH) in CH2Cl2 gives the bridged-cleaved adduct [Ru(η3 : η3-C10H16)Cl2(SHEt)], 2. Stirring of two molar equivalents of 2 in methanol with one equivalent of 1 gives the binuclear, mixed chloro/thiolato bridged compound [{Ru(η3 : η3-C10H16)Cl} 2(μ-SEt)], 3. The related doubly thiolato bridged complex [{Ru(η3 : η3-C10H10)Cl(μ-SEt)}2], 4, is formed by treatment of 1 with an excess of EtSH, or by prolonged stirring of 2 alone in methanol. Compounds 2–4 have been studied by cyclic voitammetry. Compound 2 undergoes only irreversible oxidation, whereas in the case of both 3 and 4 the observation of significant return waves is consistent with a greater stability of the primary redox products. 相似文献
15.
A series of model complexes for the type III site, in oxidised hemocyanin, containing Cu2(μ-0Ph)3+ core have been synthesised using a heptadentate ligand (H3L) formed from the Schiff base condensation of triethylenetetramine and salicylaldehyde. The ligand provides one imine and
one inbuilt imidazole nitrogen and two phenolic oxygen donors with both five- and six-membered chelate rings to each metal
centre. In the pentacoordinated complexes [Cu2(L)X]·nH2O, a third exogenous bridging ligand is present. The TG curve indicates the loss of lattice water molecules between 70 and
125°C. The residue after decomposition is CuO above 550°C. Theg values of theX-band EPR spectrum of [Cu2L(μ-OAc)]·2H2O in methanol glass (77 K) are typical of a variety of bridged copper(II) dimers. The copper-copper magnetic interaction is
dependent on the presence and nature of X in these complexes. 相似文献
16.
Shih-Hsien Hsu Yi-Wen Chiu Yu-Ling Lien Hon Man Lee Cheu-Pyeng Cheng 《Journal of organometallic chemistry》2007,692(24):5421-5428
A series of Cu(I) and Cu(II) complexes containing substituted ketiminate ligands was synthesized. Reaction of CuCl2 with 2 equiv. of Li[OC(Me)CHC(Me)N(Ar)] in toluene generated dark green solid of Cu[OC(Me)CHC(Me)N(Ar)]2 (1). Similarly, Cu(I) complex, {Cu[OC(Me)CHC(Me)N(Ar)]Li[OC(Me)CHC(Me)N(Ar)]}2 (2) was synthesized by reacting 2 equiv. of Li[OC(Me)CHC(Me)N(Ar)] with CuCl in toluene at room temperature for 12 h. While the reaction of CuCl with Li[OC(Me)CHC(Me)N(Ar)] in the presence of triphenylphosphine in THF solution at room temperature, a three-coordinated Cu[OC(Me)CHC(Me)N(Ar)](PPh3) (3) can be isolated in high yield. Replacing the PPh3 of 3 with N-heterocarbene (NHC) generates Cu[OC(Me)CHC(Me)N(Ar)](NHC) (4) in low yield. Complexes 2, 3, and 4 were characterized by 1H and 13C NMR spectroscopies and all molecules were structurally characterized by X-ray diffractometry. Two coordination modes of ketiminate ligands were found in the molecular structure of 2, one of which is copper-coordinated terminal ketiminates and the other is lithium-copper-coordinated bridging ketiminates. 相似文献
17.
A series of new manganese(I) and ruthenium(II) monometallic and bimetallic complexes made of 2,2′-bipyridine and 1,10-phenanthroline ligands, [Mn(CO)3(NN)(4,4′-bpy)]+, [{(CO)3(NN)Mn}2(4,4′-bpy)]2+ and [(CO)3(NN)Mn(4,4′-bpy)Ru(NN)2Cl]2+ (NN = 2,2′-bipyridine, 1,10-phenanthroline; 4,4′-bpy = 4,4′-bipyridine) are synthesized and characterized, in addition to already known ruthenium(II) complexes [Ru(NN)2Cl(4,4′-bpy)]+ and [Cl(NN)2Ru(4,4′-bpy)Ru(NN)2Cl]2+. The electrochemical properties show that there is a weak interaction between two metal centers in Mn–Ru heterobimetallic complexes. The photophysical behavior of all the complexes is studied. The Mn(I) monometallic and homobimetallic complexes have no detectable emission. In Mn–Ru heterobimetallic complexes, the attachment of Mn(I) with Ru(II) provides interesting photophysical properties. 相似文献
18.
We have synthesized a series of trinuclear gold(I) complexes, namely, [Au3(mu-dpmp)(S2CNR2)nCl3-n] (n = 0-3; R = Me, CH2Ph), [Au3(mu-dpmp)(mu-S2CNR2)Cl](CF3SO3) (R = Me, CH2Ph), and [Au3(mu-dpmp)(mu-S2CNMe2)(C6F5)]X (X = Cl, CF3SO3), containing the triphosphine dpmp [bis(diphenylphosphinomethyl)phenylphosphine] and varying amounts of dithiocarbamate. NMR experiments show fluxional behavior in solution for most of these derivatives because several arrangements of the ligands are possible. The crystal structure of [(mu-dpmp)(AuCl)3] has been determined by X-ray diffraction studies; the molecule displays mirror symmetry and involves an angular arrangement of the gold atoms [Au-Au-Au 119.603(14) degrees, Au-Au 3.3709(4) A]. We have studied the optical properties of these derivatives in the solid state, finding a red shift as a function of the dithiocarbamate number and, for some derivatives, wavelength-dependent emission spectra at low temperature. 相似文献
19.
Damaj Z Cisnetti F Dupont L Henon E Policar C Guillon E 《Dalton transactions (Cambridge, England : 2003)》2008,(24):3235-3245
A new family of copper(I) complexes with "glycoligands" containing a central saccharide scaffold, with 2-picolyl ether groups or 2-picolylamine or N-imidazolylamine groups, has been prepared and characterized. For this purpose, the following tetradentate ligands have been synthesized: methyl 2,3-di-O-(2-picolyl)-alpha-D-lyxofuranoside (L1), 1,5-anhydro-2-deoxy-3,4-di-O-(2-picolyl)-d-galactitol (L2), 5-(amino-N-(2-salicyl))-5-deoxy-1,2-O-isopropylidene-3-O-(2-picolyl)-alpha-D-xylofuranose (L3), and 5-(amino-N-(2-salicyl))-5-deoxy-1,2-O-isopropylidene-3-O-(methylimidazol-2-yl)-alpha-D-xylofuranose (L4). The ligands and the complexes were characterized by elemental analysis, IR, 1H and 13C NMR spectroscopies, ESI mass spectrometry, and cyclic voltammetry. Collaterally with the experimental work, HF-DFT(B3LYP/6-31G*) computations were performed to obtain additional structural information. The Cu(I) complexes are found to be pentacoordinated. The redox properties and the O2-reactivity of the Cu(I)Ln complexes have been studied. Reactions of Cu(I) complexes with dioxygen in ethanol yield stable Cu(II) complexes as confirmed by UV-visible spectrophotometry and EPR spectroscopy. 相似文献