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1.
Katerina N. Lazarou Iordanis Chadjistamatis Aris Terzis Spyros P. Perlepes Catherine P. Raptopoulou 《Polyhedron》2010
The use of succinamic acid (H2sucm) in CuII/N,N′,N″-donor [2,2′:6′,2″-terpyridine (terpy), 2,6-bis(3,5-dimethylpyrazol-1-yl)pyridine (dmbppy)] reaction mixtures yielded compounds [Cu(Hsucm)(terpy)]n(ClO4)n (1), [Cu(Hsucm)(terpy)(MeOH)](ClO4) (2), [Cu2(Hsucm)2(terpy)2](ClO4)2 (3), [Cu(ClO4)2(terpy)(MeOH)] (4), [Cu(Hsucm)(dmbppy)]n(NO3)n·3nH2O (5.3nH2O), and [CuCl2(dmbppy)]·H2O (6·H2O). The succinamate(−1) ligand exists in four different coordination modes in the structures of 1–3 and 5, i.e., the μ2-κO:κO′:κO″ in 1 and 5 which involves asymmetric chelating coordination of the carboxylato group and ligation of the amide O-atom leading to 1D coordination polymers, the μ2-κ2O:κO′ in 3 which involves asymmetric chelating and bridging coordination of the carboxylato group, and the asymmetric chelating mode in 2. The primary amide group, either coordinated in 1 and 5, or uncoordinated in 2 and 3, participate in hydrogen bonding interactions, leading to interesting crystal structures. Characteristic IR bands of the complexes are discussed in terms of the known structures and the coordination modes of the Hsucm− ligands. The thermal decomposition of complex 5·3nH2O was monitored by TG/DTG and DTA measurements. 相似文献
2.
The reactions of Mo2(O2CCH3)4 with different equivalents of N,N′-bis(pyrimidine-2-yl)formamidine (HL1) and N-(2-pyrimidinyl)formamide (HL2) afforded dimolybdenum complexes of the types Mo2(O2CCH3)(L1)2(L2) (1) trans-Mo2(L1)2(L2)2 (2) cis-Mo2(L1)2(L2)2 (3) and Mo2(L2)4 (4). Their UV–Vis and NMR spectra have been recorded and their structures determined by X-ray crystallography. Complexes 2 and 3 establish the first pair of trans and cis forms of dimolybdenum complexes containing formamidinate ligands. The L1 ligands in 1–3 are bridged to the metal centers through two central amine nitrogen atoms, while the L2 ligands in 1–4 are bridged to the metal centers via one pyrimidyl nitrogen atom and the amine nitrogen atom. The Mo–Mo distances of complexes 1 [2.0951(17) Å], 2 [2.103(1) Å] and 3 [2.1017(3) Å], which contain both Mo?N and Mo?O axial interactions, are slightly longer than those of complex 4 [2.0826(12)–2.0866(10) Å] which has only Mo?O interactions. 相似文献
3.
Angel García-Raso Juan J. Fiol Andrés Tasada Francisca M. Albertí Ferran Bádenas Xavier Solans Mercè Font-Bardia 《Polyhedron》2007
The reaction of N9,N9′-(tri or tetramethylene)-bisadenines (Ade2Cx; x = 3 or 4) in HCl 2 M at 50 °C with MCl2 · 2H2O [M = Zn(II), Cd(II)] yields outer sphere compounds like the previously described [(H-Ade)2C3][ZnCl4] · H2O (3) and [(H-Ade)2C3]2[Cd2Cl8(H2O)2] · 4H2O (4) for Ade2C3 and the new {[(H-Ade)2C4][Cd2Cl6(H2O)2] · 2H2O}n (5) for Ade2C4. On the other hand, only in case of Zn(II) complexes by changing [HCl] to 0.1 M, the inner sphere compounds [H-(Ade)2C3(ZnCl3)] (6) and [H-(Ade)2C4(ZnCl3)] · 1.5H2O (7) are obtained. X-ray diffraction study of compound 6, which represents the first inner sphere complex with a N9,N9′-bisadenine, shows a zwitterionic form with one adenine ring protonated at N(1) while the other ring is coordinated via N(7) to a ZnCl3 moiety as in other alkyl-adenine derivatives. In addition, with Ade2C4, is also possible to obtain another inner sphere complex: [(H-Ade)2C4(ZnCl3)2] · 3H2O (8). 相似文献
4.
Petr Novák Lenka Kolá?ová Jaroslav Hole?ek 《Journal of organometallic chemistry》2007,692(20):4287-4296
The set of starting tri-, di- and monoorganotin(IV) halides containing N,C,N-chelating ligand (LNCN = {1,3-[(CH3)2NCH2]2C6H3}−) has been prepared (1-5) and two compounds structurally characterized ([LNCNPh2Sn]+I3− (1c), LNCNSnBr3 (5)) in the solid state. These compounds were reacted with KF with 18-crown-6, NH4F or LCNnBu2SnF to give derivatives containing fluorine atom(s). Triorganotin(IV) fluorides LNCNMe2SnF (2a) and LNCNnBu2SnF (3a) revealed monomeric structural arrangement with covalent Sn-F bond both in the coordinating and non-coordinating solvents, except the behaviour of 3a that was ionized in the methanol solution at low temperature. The products of fluorination of LNCNSnPhCl2 (4) and 5 were described by NMR in solution as the ionic hypervalent fluorostannates or the oligomeric species reacting with chloroform, methanol or moisture to zwitterionic monomeric stannate LNCN(H)+SnF4− (5c), which was confirmed by XRD analysis in the solid state. 相似文献
5.
Guo-Lin Xu 《Journal of organometallic chemistry》2003,683(2):388-397
Three diruthenium(III) compounds Ru2(L)4Cl2, where L is mMeODMBA (N,N′-dimethyl-3-methoxybenzamidinate, 1a), DiMeODMBA (N,N′-dimethyl-3,5-dimethoxy benzamidinate, 1b), or DEBA (N,N′-diethylbenzamidinate, 1c), were prepared from the reactions between Ru2(OAc)4Cl and respective HL under reflux conditions. Metathesis reactions between 1 and LiC2Y resulted in bis-alkynyl derivatives Ru2(L)4(C2Y)2 [Y=Ph (2), SiMe3 (3), SiiPr3 (4) and C2SiMe3 (5)]. The parent compounds 1 are paramagnetic (S=1), while bis-alkynyl derivatives 2-5 are diamagnetic and display well-solved 1H- and 13C-NMR spectra. Molecular structures of compounds 1b, 1c, 2c, 3c and 4b were established through single crystal X-ray diffraction studies, which revealed RuRu bond lengths of ca. 2.32 Å for parent compounds 1 and 2.45 Å for bis-alkynyl derivatives. Cyclic voltammograms of all compounds feature three one-electron couples: an oxidation and two reductions, while the reversibility of observed couples depends on the nature of axial ligands. 相似文献
6.
Ekkehardt F. Hahn Beate Heidrich Alexander Hepp Tania Pape 《Journal of organometallic chemistry》2007,692(21):4630-4638
N-Heterocyclic carbene ligands (NHC) were metalated with Pd(OAc)2 or [Ni(CH3CN)6](BF4)2 by in situ deprotonation of imidazolium salts to give the N-olefin functionalized biscarbene complexes [MX2(NHC)2] 3-7 (3: M = Pd, X = Br, NHC = 1,3-di(3-butenyl)imidazolin-2-ylidene; 4: M = Pd, X = Br, NHC = 1,3-di(4-pentenyl)imidazolin-2-ylidene; 5: M = Pd, X = I, NHC = 1,3-diallylimidazolin-2-ylidene; 6: M = Ni, X = I, NHC = 1,3-diallylimidazolin-2-ylidene; 7: M = Ni, X = I, NHC = 1-methyl-3-allylimidazolin-2-ylidene). Molecular structure determinations for 4-7 revealed that square-planar complexes with cis (5) or trans (4, 6, 7) coordination geometry at the metal center had been obtained. Reaction of nickelocene with imidazolium bromides afforded the η5-cyclopentadienyl (η5-Cp) monocarbene nickel complexes [NiBr(η5-Cp)(NHC)] 8 and 9 (8: NHC = 1-methyl-3-allylimidazolin-2-ylidene; 9: NHC = 1,3-diallylimidazolin-2-ylidene). The bromine abstraction in complexes 8 and 9 with silver tetrafluoroborate gave complexes [NiBr(η5-Cp)(η3-NHC)] 10 and 11. The X-ray structure analysis of 10 and 11 showed a trigonal-pyramidal coordination geometry at the nickel(II) center and coordination of one N-allyl substituent. 相似文献
7.
Schiff base N,N′-bis(salicylidene)-p-phenylenediamine (LH2) complexed with Pt(en)Cl2 and Pd(en)Cl2 provided [Pt(en)L]2 · 4PF6 (1) and Pd(Salen) (2) (Salen = N,N′-bis(salicylidene)-ethylenediamine), respectively, which were characterized by their elemental analysis, spectroscopic data and X-ray data. A solid complex obtained by the reaction of hexafluorobenzene (hfb) with the representative complex 1 has been isolated and characterized as 3 (1 · hfb) using UV–Vis, NMR (1H, 13C and 19F) data. A solid complex of hfb with a reported Zn-cyclophane 4 has also been prepared and characterized 5 (4 · hfb) for comparison with complex 3. The association of hfb with 1 and 4 has also been monitored using UV–Vis and luminescence data. 相似文献
8.
Reaction of Ln(NO3)3·6H2O with H2L [H2L=N,N′-bis(salicylidene)propane-1,2-diamine] gives rise to five new coordination polymers, viz. [Pr(H2L)(NO3)3(MeOH)]n (1) and [Ln(H2L)1.5(NO3)3]n [Ln=La (2), Eu (3), Sm (4) and Gd (5)]. Crystal structural analysis reveals that H2L effectively functions as a bridging ligand forming one-dimensional (1D) chain and two-dimensional (2D) open-framework polymers. Solid-state fluorescence spectra of 3 and 4 exhibit typical red fluorescence of Eu(III) and Sm(III) ions at room temperature while 2 emits blue fluorescence of ligand H2L. The lowest triplet level of ligand H2L was calculated on the basis of the phosphorescence spectrum of 5. The energy transfer mechanisms in the lanthanide polymers were described and discussed. 相似文献
9.
Complexes of ZnII salts with 4,4′-bipyridine-N,N′-dioxide (bpdo) have been prepared by solvathermal and solvent layering methods. Three complexes were obtained from ZnBr2: 1 is a 2D coordination polymer [Zn2Br4(bpdo)2]n, (2) a discrete trimetallic molecule [Zn3Br6(H2O)2(bpdo)4] and 3 a salt [ZnBr4][Zn(H2O)5(bpdo)]. Complexes 2 and 3 contain ZnII ions in both octahedral and tetrahedral coordination geometry. While in 2, these are covalently linked by bridging bpdo ligands forming zwitterionic trimetallic molecules, in 3 there is complete charge separation into [ZnBr4]2− anions and [Zn(H2O)5(bpdo)]2+ cations. When Zn(NCS)2 is used as starting material, a 1D coordination polymer [Zn(H2O)2 (bpdo)(NCS)2]n is obtained. 相似文献
10.
Shin-ichi NayaMakoto Nitta 《Tetrahedron》2003,59(21):3709-3718
Novel condensation reaction of tropone with N-substituted and N,N′-disubstitued barbituric acids in Ac2O afforded 5-(cyclohepta-2′,4′,6′-trienylidene)pyrimidine-2(1H),4(3H),6(5H)-trione derivatives (8a-f) in moderate to good yields. The 13C NMR spectral study of 8a-f revealed that the contribution of zwitterionic resonance structures is less important as compared with that of 8,8-dicyanoheptafulvene. The rotational barriers (ΔG‡) around the exocyclic double bond of mono-substituted derivatives 8a-c were obtained to be 14.51-15.03 kcal mol−1 by the variable temperature 1H NMR measurements. The electrochemical properties of 8a-f were also studied by CV measurement. Upon treatment with DDQ, 8a-c underwent oxidative cyclization to give two products, 7 and 9-substituted cyclohepta[b]pyrimido[5,4-d]furan-8(7H),10(9H)-dionylium tetrafluoroborates (11a-c·BF4− and 12a-c·BF4−) in various ratios, while that of disubstituted derivatives 8d-f afforded 7,9-disubstituted cyclohepta[b]pyrimido[5,4-d]furan-8(7H),10(9H)-dionylium tetrafluoroborate (11d-f·BF4−) in good yields. Similarly, preparation of known 5-(1′-oxocycloheptatrien-2′-yl)-pyrimidine-2(1H),4(3H),6(5H)-trione derivatives (14a-d) and novel derivatives 14e,f was carried out. Treatment of 14a-c with aq. HBF4/Ac2O afforded two kinds of novel products 11a-c·BF4− and 12a,c·BF4− in various ratios, respectively, while that of 14d-f afforded 11d-f. The product ratios of 11a-c·BF4− and 12a-c·BF4− observed in two kinds of cyclization reactions were rationalized on the basis of MO calculations of model compounds 20a and 21a. The spectroscopic and electrochemical properties of 11a-f·BF4− and 12a-c·BF4− were studied, and structural characterization of 11c·BF4− based on the X-ray crystal analysis and MO calculation was also performed. 相似文献
11.
Elena Mas-Marzá Eduardo Peris Beatriz Royo 《Journal of organometallic chemistry》2006,691(12):2708-2712
Compound MoO2Cl2(THF)2 reacts with two equivalents of 1,3-dialkyl substituted 4,5-dimethylimidazol-2-ylidenes to give the dioxomolybdenum(VI) complexes MoO2Cl2(LR)2 [R = Me (1), i-Pr (2)]. Treatment of MoO2Cl2(THF)2 with one equivalent of the N-heterocyclic carbenes LMe, Li-Pr and C1Ln-Bu (LMe = 1,3,4,5-tetramethylimidazol-2-ylidene, Li-Pr = 1,3-diisopropyl-4,5-dimethylimidazol-2-ylidene, and C1Ln-Bu = 1,3-dibutyl-4,5-dichloroimidazol-2-ylidene) affords the monocarbene adducts MoO2Cl2(LR) [R = Me (3), i-Pr (4)] and MoO2Cl2(C1Ln-Bu) (5), respectively. Decomposition of complexes 1-5 affords a molybdenum oxychloride anion [Mo2O5Cl4]2− as an imidazolium salt. 相似文献
12.
13.
Akira Yogi Jae-Hwan Oh Takanori Nishioka Rika Tanaka Eiji Asato Isamu Kinoshita Satoshi Takara 《Polyhedron》2010
The syntheses and characterization of novel ruthenium(II) complexes containing bis(3,5-dimethylpyrazol-1-yl)acetato (bdmpza), a new class of scorpionate ligands, are reported herein. [RuCl(bdmpza)(η4-1,5-cyclooctadiene)] (1) was found to be a versatile precursor to synthesize a wide range of new ruthenium(II) complexes with the bdmpza ligand. The treatment of 1 with pyridine (py), diphenylphosphinoethane (dppe), 2,2′-bipyridyl (bpy), 1,10-phenanethroline (phen), or bispicolylamine (Hbpica) in refluxing N,N-dimethylformamide resulted in displacement of the 1,5-cyclooctadiene ligand to afford [RuCl(bdmpza)(py)2] (2), [RuCl(bdmpza)(dppe)] (3), [RuCl(bdmpza)(bpy)] (4), [RuCl(bdmpza)(phen)] (5), and [Ru(bdmpza)(Hbpica)]Cl (6Cl) in good yields, respectively. The structures of 1–4, and 6 were determined by X-ray structure analyses. 相似文献
14.
Yoshikatsu Ito 《Tetrahedron》2007,63(15):3108-3114
Photocarboxylation of 1,1-diphenylethylene with N,N,N′,N′-tetramethylbenzidine (TMB) in MeCN under bubbling of CO2 proceeded with high catalytic efficiency, giving 3,3-diphenylacrylic acid (DPA) and 3-hydroxy-3,3-diphenylpropionic acid (20). The turnover number (TON=(DPA+20)/TMB) reached 17. Similarly, 1-phenyl-1-cyclohexene yielded cis-2-acetamido-2-phenylcyclohexanecarboxylic acid with TON 5.9. As compared with related N,N-dimethylaniline derivatives, TMB is more resistant to photodecomposition, has the much larger absorbance in the S0→S1 transition, and has the lower quenching efficiency by CO2. Probably these factors are partly responsible for the high TON observed for TMB. 相似文献
15.
The C,N-(trimethylsilyliminodiphenylphosphoranyl)silylmethylmetal complexes [Fe(L)2] (3), [Co(L)2] (4), [ZrCl3(L)]·0.83CH2Cl2 (5), [Fe(L)3] (6), [Fe(L′)2] (7) and [Co(L′)2] (8) have been prepared from the lithium compound Li[CH(SiMe2R)P(Ph)2NSiMe3] [1a, (R = Me) {≡ Li(L)}; 1b, (R = NEt2) {≡ Li(L′)}] and the appropriate metal chloride (or for 7, FeCl3). From Li[N(SiMe3)C(Ph)C(H)P(Ph)2NSiMe3] [≡ Li(L″)] (2), prepared in situ from Li(L) (1a) and PhCN, and CoCl2 there was obtained bis(3-trimethylsilylimino- diphenylphosphoranyl-2-phenyl-N-trimethylsilyl-1-azaallyl-N,N′)cobalt(II) (9). These crystalline complexes 3-9 were characterised by their mass spectra, microanalyses, high spin magnetic moments (not 5) and for 5 multinuclear NMR solution spectra. The X-ray structure of 3 showed it to be a pseudotetrahedral bis(chelate), the iron atom at the spiro junction. 相似文献
16.
M.C. Torralba J.A. Campo E. Pinilla M.R. Torres 《Journal of organometallic chemistry》2006,691(4):765-778
Two types of Pd-complexes containing the new N,N′-ligands 2-[3-(4-alkyloxyphenyl)pyrazol-1-yl]pyridine (pzRpy; R = C6H4OCnH2n+1, n = 6 (hp), 10 (dp), 12 (ddp), 14 (tdp), 16 (hdp), 18 (odp)) (1-6), namely c-[Pd(Cl)2(pzRpy)] (7-10) and c-[Pd(η3-C3H5)(pzRpy)]BF4 (11-16), have been synthesised and characterised by different spectroscopic techniques. Those members of the second type containing the largest chains (R = ddp 13, tdp 14, hdp 15, odp 16) have been found to have liquid crystal properties showing smectic A mesophases. By contrast, neither the free ligands pzRpy nor their related c-[Pd(Cl)2(pzRpy)] complexes exhibited mesomorphism. The new synthesised metallomesogens are mononuclear complexes with an unsymmetrical molecular shape as deduced from the X-ray structures of c-[Pd(η3-C3H5)(pzRpy)]BF4 (R = hp, 11; dp, 12). Both compounds, which are isostructural, show a distorted square-planar environment on the palladium centres defined by the allyl and the bidentate pzRpy ligands. The crystal structure reveals that both the counteranion and the pzRpy ligand function as a source of hydrogen-bonding and intermolecular π?π contacts resulting in a 2D supramolecular assembly. 相似文献
17.
18.
Terézia Szabó-PlánkaJán Moncol Eszter TóthBéla Gyurcsik Nóra Veronika NagyZuzana Vasková Antal RockenbauerDušan Valigura 《Polyhedron》2011,30(14):2421-2429
EPR simulation method together with pH-potentiometry combined with UV-Vis spectrophotometry were used for the study of the ternary system 4-fuorosalicylic acid (HA)-N,N-diethylnicotinamide (B)-copper(II) in aqueous solution. The N,N-diethylnicotinamide ligand is a weak donor, its mixed-ligand complexes with 4-fluorosalicylate anions are more favoured. The number of coordinated N,N-diethylnicotinamide molecules increases with decreasing temperature: up to four ones were detected in the coordination sphere of copper(II) in frozen solutions. The formation of [CuH−1AB2] and [CuH−1A] was detected by all methods at neutral pH. At lower pH values, [CuA2B2] and [CuB] become dominant, and this fact is in good agreement with [CuA2B2(H2O)2] crystals obtained from similar solutions. The structural unit of the [CuA2B2(H2O)2] complex consists of a copper(II) ion, which is monodentately coordinated by a pair of 4-fluorosalicylate anions and by a pair of N,N-diethylnicotinamide in trans positions in the basal plane, and by two water molecules in the axial positions of a tetragonal bipyramid. 相似文献
19.
Using Cu(II), Mn(II) or Co(II) salt and the flexible ligands, N-[(4-carboxyphenyl)-sulfonyl]glycine (H3L1) and N-[(3-carboxyphenyl)-sulfonyl]glycine (H3L2), a series of new coordination polymers, [Mn(phen)(H2O)4][HL1] (1), [Co3(L1)2(bipy)3(H2O)6]n·8nH2O (2), [Cu4(L1)2(OH)2(bipy)4]n·12nH2O (3), [Na(H2L1)(H2O)]n (4), [Mn2(HL2)2(dpe)3(H2O)2]n·ndpe (5), (phen = 1,10-phenanthroline, bipy = 4,4′-bipyridine, dpe = 1,2-di(4-pyridyl)ethylene), varying from 0D to 3D, have been synthesized and structurally characterized. Compound 1 has a [Mn(phen)(H2O)4]2+ cation and a HL12− anion. Compound 2 features a new 1D triple chain, based on octahedral cobalt atoms bridged by bipy molecules and terminally coordinated by two H3L1 ligands. Compound 3 has a 2D layered structure, constructed from new alternating chains where H3L1, hydroxyl and water molecules simultaneously act as bridging ligands. Compound 4 possesses a bilayer structure in which two adjacent layers are pillared by H3L1 ligands into a 2D bilayer network. Compound 5 is a unique 3D coordination polymer in which each Mn center binds two trans-located dpe molecules. The thermal stability as well as magnetic properties of 5 was also studied. This work and our previous work indicate that the positional isomer of the anionic N-[(carboxyphenyl)-sulfonyl]glycine is important in the construction of these network structures, which are also significantly regulated by the metal centers. 相似文献
20.
Sanjay K Singh 《Journal of organometallic chemistry》2004,689(12):2073-2079
The synthesis and characterization of binuclear ruthenium complexes [{(η6-C6H6)Ru}2(μ-bsh)2] (1), [{(η6-C10H14)Ru}2(μ-bsh)2] (2), [{(η6-C6Me6)Ru}2(μ-bsh)2] (3), and rhodium complex [{(η5-C5Me5)RhCl}2(μ-bsh)] (4) (bsh=N,N′-bis(salicylidine)-hydrazine dianion) are reported. The complexes have been fully characterized by analytical and spectral techniques and unusual coordination mode of the ligand H2bsh has been confirmed by single crystal X-ray analysis of the complex 2. Structural data revealed extensive inter- and intra-molecular C-H?O and C-H?π interactions and involvement of methyl and isopropyl hydrogen from the p-cymene in hydrogen bonding. 相似文献