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1.
A series of pyrazole-bridged heterometallic 3d-4f complexes, [CuDy(ipdc)2(H2O)4] · (2H2O)(H3O+) (1) and [CuLn(pdc)(ipdc)(H2O)4] · H3O+ (Ln = Ho (2), Er (3), Yb (4); H3ipdc = 4-iodo-3,5-pyrazoledicarboxylic acid; H3pdc = 3,5-pyrazoledicarboxylic acid), {[Cu3Ln4(ipdc)6(H2O)16] · xH2O}n (Ln = Sm (5), x = 8.5; Ln = Eu (6), x = 7; Ln = Gd (7), Tb (8), x = 9), have been synthesized and structurally characterized. Ligand H3ipdc was in situ obtained by iodination of ligand H3pdc. Complexes 1-4 are pyrazole-bridged heterometallic dinuclear complexes, and 2-4 are isostructural. Complexes 5-8 are isostructural and comprised of an unusual infinite one-dimensional tape-like chain based on pyrazole-bridged heterometallic dinuclear units. The magnetic properties of compounds 1-4, 7 and 8 have been investigated through the magnetic measurement over the temperature range of 1.8-300 K. 相似文献
2.
Thiocarbonate ruthenium complexes of the form CpRu(L)(L′)SCO2R (L = L′ = PPh3 (1), 1/2 dppe (2), L = PPh3, L′ = CO (3); R = Et (a), Bun (b), C6H5 (c), 4-C6H4NO2 (d)) have been synthesized by the reaction of the corresponding sulfhydryl complexes, CpRu(L)(L′)SH, with chloroformates, ROCOCl, at low temperature. The bis(triphenylphosphine) complexes 1 can be converted to 3 under CO atmosphere. The crystal structures of CpRu(PPh3)2SCO2Bun (1b), CpRu(dppe)SCO2Bun (2b), and CpRu(PPh3)(CO)SCO2Bun (3b) are reported. 相似文献
3.
Daisuke Kanamori 《Inorganica chimica acta》2005,358(2):331-338
Iron(III) porphinate complexes of phenolate that have NH?O hydrogen bonds on the coordinating oxygen, [FeIII(OEP){O-2,6-(RCONH)2C6H3}] (R = CF3 (1), CH3 (3)) and [FeIII(OEP)(O-2-RCONHC6H4)] (R = CF3 (2), CH3 (4)) (OEP = 2,3,7,8,12,13,17,18-octaethyl-21H, 23H-porphinato), were synthesized and characterized as models of heme catalase. The presence of NH?O hydrogen bonds was established by their crystal structures and IR shifts of the amide NH band. The crystal structure of 1 shows an extremely elongated Fe-O bond, 1.926(3) Å, compared to 1.887(2) Å in 2 or 1.848(4) Å in [FeIII(OEP)(OPh)]. The NH?O hydrogen bond decreases an electron donation from oxygen to iron, resulting in a long Fe-O bond and a positive redox potential. 相似文献
4.
Roderick C. Jones Michael G. Gardiner Vicki-Anne Tolhurst 《Inorganica chimica acta》2010,363(1):77-295
Ligands containing the 2-organochalcogenomethylpyridine motif with substituents in the 4- or 6-position of the pyridyl ring, R4,R6-pyCH2ER1 [R4 = R6 = H, ER1 = SMe (1), SeMe (2), SPh (6), SePh (7); R4 = Me, R6 = H, ER1 = SMe (3), SPh (8), SePh (9); R4 = H, R6 = Me, ER1 = SMe (4), SPh (10), SePh (11); R4 = H, R6 = Ph, ER1 = SMe (5), SPh (12), SePh (13)] are obtained on the reaction of R4,R6-pyMe with LiBun followed by R1EER1. On reaction with PdCl2(NCMe)2, the ligands with a 6-phenyl substituent form cyclopalladated species PdCl{6-(o-C6H4)pyCH2ER1-C,N,E} (5a, 12a, 13a) with the structure of 13a (ER1 = SePh) confirmed by X-ray crystallography; other ligands form complexes of stoichiometry PdCl2(R4,R6-pyCH2ER1). Complexes with R6 = H are monomeric with N,E-bidentate configurations, confirmed by structural analysis for 3a (R4 = Me, ER1 = SMe), 7a (R4 = H, ER1 = SePh) and 9a (R4 = Me, ER1 = SePh). Two of the 6-methyl substituted complexes examined by X-ray crystallography are oligomeric with trans-PdCl2(N,E) motifs and bridging ligands, trimeric [PdCl2(μ-6-MepyCH2SPh-N,S)]3 (10a) and dimeric [PdCl2(μ-6-MepyCH2SePh-N,Se)]2 (11a). This behaviour is attributed to avoidance of the Me···Cl interaction that would occur in the cis-bidentate configuration if the pyridyl plane had the same orientation with respect to the coordination plane as observed for 3a, 7a and 9a [dihedral angles 8.0(2)-16.8(2)°]. When examined as precatalysts for the Mizoroki-Heck reaction of n-butyl acrylate with aryl halides in N,N-dimethylacetamide at 120 °C, the complexes exhibit the anticipated trends in yield (ArI > ArBr > ArCl, higher yield for electron withdrawing substituents in 4-RC6H4Br and 4-RC6H4Cl). The most active precatalysts are PdCl2(R4-pyCH2SMe-N,S) (R = H (1a), Me (3a)); complexes of the selenium containing ligands exhibit very low activity. For closely related ligands, the changes SMe to SPh, 6-H to 6-Me, and 6-H to 6-Ph lead to lower activity, consistent with involvement of both the pyridyl and chalcogen donors in reactions involving aryl bromides. The precatalyst PdCl2(pyCH2SMe-N,S) (1a) exhibits higher activity for the reaction of aryl chlorides in Bun4NCl at 120 °C as a solvent under non-aqueous ionic liquid (NAIL) conditions. 相似文献
5.
Yanxiang Cheng 《Inorganica chimica acta》2009,362(13):4678-4684
The crystalline compounds [LnCl2(L)(thf)2] [Ln = Ce (1), Tb (2), Yb (3)], [NdI2(L)(thf)2] (4), [LnCl(L′)2] [Ln = Tb (5), Yb (6) (a known compound)] and [YbCl(L′′)(μ-Cl)2Li(OEt2)2] (7) have been prepared [L = {N(C6H3Pri2-2,6)C(H)}2CPh, L′ = {N(SiMe3)C(Ph)}2CH, L′′ = {N(SiMe3)C(C6H4Ph-4)}2CH]. The X-ray molecular structures of 2-7 have been established; in each, the monoanionic ligand L, L′ or L′′ is N,N′-chelating and essentially π-delocalised. Each of 1-7 was prepared from the appropriate LnCl3, or for 4 [NdI3(thf)2], and an equivalent portion of the appropriate alkali metal [Li for 7, Na for 2, 3 and 5, or K for 1, 4 and 6] β-diiminate in thf; the isolation of exclusively 5 and 6 (rather than the L′ analogues of 2 or 3) is noteworthy, as is the structure of 7 which has no precedent in Group 3 or 4f metal β-diiminato chemistry. 相似文献
6.
By applying the hydrothermal in situ acylation reactions between alkyl-substituted pyridine-2,3-dicarboxylic acids and hydrazine hydrate, six pyridine-monoacylhydrazidate-coordinated transition-metal complexes [Mn(MPDH)2] 1, [M(MPDH)2(H2O)2]·2H2O (M2+ = Co2+2, Zn2+3), [Mn(EPDH)2(H2O)2] 4 and [M(EPDH)2(H2O)2] (M2+ = Zn2+5, Co2+6) (MPDH = 6-methylpyridine-2,3-dicarboxylhydrazidate; EPDH = 5-ethylpyridine-2,3-dicarboxylhydrazidate) were obtained. Although only compound 1 is a 1-D chained coordination polymer and the others are the mononuclear molecular entities, they all further self-assemble into the interesting supramolecular networks via hydrogen-bonded interactions between pyridine-monoacylhydrazidate ligands. Two Zn2+ compounds 3 and 5 possess the fluorescence properties with maximum emissions at 517 nm for 3 and 530 nm for 5 upon excitation, respectively. The magnetic analysis for compound 1 indicates there exists the antiferromagnetic interactions between the Mn(II) ions. 相似文献
7.
Substitution reaction of chloro η6-arene ruthenium N∩O-base complexes [(η6-arene)Ru(N∩O)Cl] [N∩O = pyrazine-2-carboxylic acid (pca-H), 8-hydroxyquinoline (hq-H); arene = p-iPrC6H4Me, N∩O = hq (1); arene = C6Me6, N∩O = hq (2)] with NaN3 yield the neutral arene ruthenium azido complexes of the general formula [(η6-arene)Ru(N∩O)N3] [N∩O = pca, arene = p-iPrC6H4Me (3), arene = C6Me6 (4); N∩O = hq, arene = p-iPrC6H4Me (5), arene = C6Me6 (6)]. These complexes undergo [3 + 2] dipolar cycloaddition reaction with activated alkynes dimethyl and diethyl acetylenedicarboxylates to yield the arene triazole complexes [(η6-arene)Ru(N∩O){N3C2(CO2R)2}] [N∩O = pca, R = Me, arene = p-iPrC6H4Me (7), C6Me6 (8); R = Et, arene = p-iPrC6H4Me (9), C6Me6 (10); N∩O = hq, R = Me, arene = p-iPrC6H4Me (11) C6Me6 (12); R = Et, arene = p-iPrC6H4Me (13), C6Me6 (14)]. On the bases of proton NMR study, in the above triazole complexes N(2) isomers are assigned with dimethylacetylenedicarboxylate whereas N(1) isomers with diethylacetylenedicarboxylate. All complexes have been characterized by IR and NMR spectroscopy as well as by elemental analysis. The molecular structures of the azido complexes [(η6-p-iPrC6H4Me)Ru(pca)N3] (3), [(η6-p-iPrC6H4Me)Ru(hq)N3] (5) and [(η6-C6Me6)Ru(hq)N3] (6) have been established by single crystal X-ray diffraction studies. 相似文献
8.
Four new zinc(II) cyclams of the composition {Zn(L)(tp2−) · H2O}n (1), {Zn(L)(H2bta2−) · 2H2O}n (2), [Zn2(L)2(ox2−)] 2ClO4 · 2DMF (3), and Zn(L)(H2btc−)2 · 2DMF (4), where L = cyclam, tp2− = 1,4-benzenedicarboxylate ion, H2bta2− = 1,2,4,5-benzenetetracarboxylate ion, ox2− = oxalate ion, DMF = N,N-dimethylformamide, and H2btc− = 1,3,5-benzenetricarboxylate ion, have been synthesized and structurally characterized by a combination of analytical, spectroscopic and crystallographic methods. The carboxylato ligands in the complexes 1-4 show strong coordination tendencies toward zinc(II) cyclams with hydrogen bonding interactions between the pre-organized N-H groups of the macrocycle and oxygen atoms of the carboxylato ligands. The macrocycles in 1, 2, and 4 adopt trans-III configurations with the appropriate R,R,S,S arrangement of the four chiral nitrogen centers, respectively. However, the complex 3 shows an unusual cis V conformation with the R,R,R,R nitrogen configuration. The finding of strong interactions between the carboxylato ligands and the zinc(II) ions may provide additional knowledge for the improved design of receptor-targeted zinc(II) cyclams in anti-HIV agents. 相似文献
9.
Tanmay K. Jana Rabindranath Pradhan Subhajit Dinda Corine Simonnet Inhar Imaz Léopold Fournès Francis Sécheresse Ramgopal Bhattacharyya 《Inorganica chimica acta》2009,362(10):3583-3594
Iron (II) and iron (III) complexes, [FeII(DEDTC)2(dppe)] · CH2Cl2 (1), [FeII(ETXANT)2(dppe)] (2) (DEDTC = diethyldithiocarbamate, ETXANT = ethyl xanthate, dppe = 1,2-bis (diphenylphosphino) ethane), and [FeIII(DEDTC)2(dppe)] [FeIIICl4] (3) have been synthesized and characterized. Since 3 contains two magnetic centers, an anion metathesis reaction has been conducted to replace the tetrahedral FeCl4− by a non-magnetic BPh4− ion producing [FeIII(DEDTC)2(dppe)]BPh4 (4) for the sake of unequivocal understanding of the magnetic behavior of the cation of 3. With the similar end in view, the well-known FeCl4− ion, the counter anion of 3, is trapped as PPh4[FeIIICl4] (5) and its magnetic property from 298 to 2 K has been studied. Besides the spectroscopic (IR, UV-Vis, NMR, EPR, Mass and XPS) characterization of the appropriate compounds, especially 2, others viz. 1, 3 and 4 have been structurally characterized by X-ray crystallography. While FeII complexes, 1 and 2, are diamagnetic, the FeIII systems, namely the cations of 3, and 4 behave as low-spin (S = 1/2) paramagnetic species from 298 to 50 K. Below 50 K 3 shows gradual increase of χMT up to 2 K suggesting ferromagnetic behavior while 4 exhibits gradual decrease of magnetic moment from 60 to 2 K, indicating the occurrence of weak antiferromagnetic interaction. These conclusions are supported by the Mössbauer studies of 3 and 4. The Mössbauer pattern of 1 exhibits a doublet site for diamagnetic (2-400 K) FeII. The compounds 1, 2 and 4 encompass interesting cyclic voltammetric responses involving FeII, FeIII and FeIV. 相似文献
10.
Santiago Gómez-Ruiz Sanjiv Prashar Mariano Fajardo Antonio Otero 《Inorganica chimica acta》2009,362(4):1042-3345
The ansa-titanocene complexes, [Ti{Me2Si(η5-C5Me4)(η5-C5H3R)}Cl2] (R = Me (5), iPr (6), tBu (7), SiMe3 (8)), were obtained from the reaction of Li2{Me2Si(C5Me4)(C5H3R)} (R = Me (1), iPr (2), tBu (3), SiMe3 (4)) with [TiCl4(THF)2], respectively. Compounds 5-8 have been tested as catalysts in the polymerization of ethylene and compared with the ansa-titanocene complexes [Ti{Me2Si(η5-C5H4)2}Cl2] and [Ti{Me2Si(η5-C5Me4)(η5-C5H4)}Cl2]. The resulting polyethylene showed molecular weights of about 200 000 g mol−1 and polydispersity values of approximately 3. In addition, the molecular structure of 6 has been determined by single crystal X-ray diffraction studies. 相似文献
11.
Three water-soluble dicobalt(III) complexes, [Co2L2(µ-OH)2](ClO4)2·5H2O (1), [Co2L2(µ-OH)2](ClO4)2·CH3OH·H2O(2); [Co2L2(µ-OH)2](ClO4)2·4H2O(3) (L = 1,4,7-triazacyclononane-N-acetate monoanion), were prepared to serve as nuclease mimics. The complexes were characterized by X-ray, IR and UV-vis spectroscopy as well as ESI-MS. Three complexes exhibit similar structures, just with different solvent molecules. The electrospray mass spectrum of 1 in solution indicates that dinuclear ion [Co2L2(µ-OH)2-H+] + (4) is the active species. In the absence of any reducing agent, the complexes cleave plasmid pBR322 DNA was performed and its hydrolytic mechanism was demonstrated with radical scavengers, anaerobic reaction and T4 ligase. The kinetic aspects of DNA cleavage under pseudo- or true-Michaelis-Menten conditions are also detailed, kinetic parameters (kcat, KM) were calculated to be 3.57 h− 1, 6.92 × 10− 4 M; 0.28 h− 1, 1.9 × 10− 5 M for 4, respectively. 相似文献
12.
Six lanthanide two-dimensional network coordination polymers with the general formula of [Ln(pmida)(NO3)(H2O)]n, where Ln = La (1), Nd (2), Sm (3), Gd (4), Dy (5), Er (6) and pmida2− = N-(2-pyridylmethyl)iminodiacetate, have been synthesized by hydrothermal process and characterized by elemental analysis, Infrared spectroscopy, thermogravimetric analysis and single-crystal X-ray diffraction. All crystals are isostructural and crystallize in the monoclinic space group P21/a. The lanthanide(III) ion is nine-coordinated in a geometry of distorted tricapped trigonal prism by two N atoms and two O atoms from one pmida2− ligand, two bridging carboxylate O atoms from other two pmida2− ligands, two O atoms of a bidentate chelating nitrate and a O atom of a coordinated water molecule. The luminescent properties of [Sm(pmida)(NO3)(H2O)]n (3) and [Dy(pmida)(NO3)(H2O)]n (5) were investigated. 相似文献
13.
A series of organotin(IV) complexes with Schiff base ligand pyruvic acid 3-hydroxy-2-naphthoyl hydrazone [R2SnLY]2, L = 3-HO-C10H6-2-CONHNC(CH3)COOH, R = n-C4H9, Y = CH3OH (1), R = n-C4H9, Y = N (2), R = PhCH2 (3), R = Ph, Y = CH3OH (4), R = Me, (5) and [R3SnLY], L = 3-HO-C10H6-2-CONHNC(CH3)COOH, R = n-C4H9, Y = H2O, (6), R = Ph (7), R = Me (8) have been synthesized. These complexes have been characterized by elemental analysis, IR, 1H and 119Sn NMR spectra. The crystal and molecular structure of complexes 1, 2 and 6 have been determined by X-ray single crystal diffraction. Results showed that complex 1 has a dimeric structure and the central tin atom is rendered seven-coordinate in a distorted pentagonal-bipyramid configuration. The complex 2 has a monoclinic structure and the central tin atom is rendered six-coordinate in octahedrally configuration with a planar of SnO3N unit and two apical aryl C atoms. And the whole structure consists of molecular units connected by weak intermolecular Sn?N and O-H?N interactions. In the complex 6, the central tin atom is five-coordinate in distorted trigonal-bipyramidal geometry. 相似文献
14.
Neutral dioxovanadium (V) complexes [VO2(HL)] (H2L = I: 1, H2L = II: 2 and H2L = III: 3; H2L are the thiosemicarbazones H2pydx-tsc (I), H2pydx-chtsc (II) and H2pydx-clbtsc (III); pydx = pyridoxal, tsc = thiosemicarbazide, chtsc = N4-cyclohexylthiosemicarbazide, clbtsc = N4-(2-chloro)benzylthiosemicarbazide) have been isolated and characterised on the basis of elemental and electrochemical analyses, spectroscopic (IR, UV-Vis, 1H and 51V NMR) data, thermogravimetric studies and reactivity patterns. These complexes are stable in solution at ambient temperature but heating of the methanolic solutions yields the μ-oxo binuclear complexes [(VOL)2μ-O] (H2L = I: 4, H2L = II: 5, H2L = III: 6). Treatments of dioxo species with H2O2 yield oxoperoxo species, the formations of which have been established spectrophotometrically. Similarly, the formations of oxohydroxo species, an intermediate proposed during the catalytic action of haloperoxidases, have also been established in solution by treating 1, 2 and 3 with a methanolic solution of HCl. The antiamoebic activities were carried out to ascertain the effectiveness of dioxovanadium(V) and μ-oxobis(oxovanadium(V)) complexes in comparison to their corresponding thiosemicarbazones. These complexes possess noteworthy potencies against HM1:1MSS strain of Entamoeba histolytica. Complexes 2, 3, 5 and 6 showed less IC50 values than metronidazole, indicating that these metal thiosemicarbazones may be the lead molecules to inhibit the growth of E. histolytica. Within the series, complex 5 showed the most promising amoebicidal activity (IC50 = 0.5 μM versus IC50 = 1.8 of metronidazole). 相似文献
15.
Five new supramolecular lanthanide coordination polymers with three different structures, {[La2(IA)3(phen)2] · 2H2O}n (1), {[Ln(IA)1.5(phen)] · xH2O}n [x = 1, Ln = Eu (2); x = 0.25, Ln = Dy (3)], and [Ln(IA)1.5(phen)]n [Ln = Er (4); Yb (5)], were prepared by hydro- and solvothermal reactions of lanthanide chlorides with itaconic acid (H2IA) and 1,10-phenanthroline (phen), and structurally characterized by single crystal X-ray diffraction. 1 Comprises 1-D double-chains that are further assembled to a 3-D supramolecular structure via hydrogen bonds and π-π stacks between phen molecules. 2 and 3 have 2-D infinite networks which are further constructed to form 3-D supramolecular architectures with 1-D channels by π-π aromatic interactions. 4 and 5 have 2-D layer structures consisting of three types of rings which are further architectured to form 3-D supramolecular structures by C-H?O hydrogen bonds. The H2IA ligands are all completely deprotonated and exhibit tetra-, penta-, and hexadentate coordination modes in the titled complexes. The high-resolution emission spectrum of 2 shows only one Eu3+ ion site in 2, which is in agreement with the result of X-ray diffraction. And the magnetic property and the thermal stability of 2 were also investigated. 相似文献
16.
Damián Fernández 《Inorganica chimica acta》2005,358(9):2575-2584
The distorted square-planar complexes [Pd(PNHP)Cl]Cl (1) (PNHP = bis[2-(diphenylphosphino)ethyl]amine), [M(P3)Cl]Cl [P3 = bis[2-(diphenylphosphino)ethyl]phenylphosphine; M = Pd (2), Pt (3)] and [Pt(NP3)Cl]Cl (5) (NP3 = tris[2-(diphenylphosphino)ethyl]amine), coexisting in the later case with a square-pyramidal arrangement, react with one equivalent of CuCl to give the mononuclear heteroionic systems [M(L)Cl](CuCl2) [L = PNHP, M = Pd (1a); L = P3, M = Pd (2a), Pt (3a); L = NP3, M = Pt (5a)]. The crystal structure of 3a confirms that Pt(II) retains the distorted square-planar geometry of 3 in the cation with P3 acting as tridentate chelating ligand, the central P atom being trans to one chloride. The counter anion is a nearly linear dichlorocuprate(I) ion. However, the five-coordinate complexes [Pd(NP3)Cl]Cl (4), [M(PP3)Cl]Cl (M = Pd (6), Pt (7); PP3 = tris[2-(diphenylphosphino)ethyl] phosphine) containing three fused five-membered chelate rings undergo a ring-opening by interaction with one (4, 6, 7) and two (6, 7) equivalents of CuCl with formation of neutral MCu(L)Cl3 [L = NP3, M = Pd (4a); L = PP3, M = Pd (6a), Pt (7a)] and ionic [MCu(PP3)Cl2](CuCl2) [M = Pd (6b), Pt (7b)] compounds, respectively. The heteronuclear systems were shown by 31P NMR to have structures where the phosphines are acting as tridentate chelating ligands to M(II) and monodentate bridging to Cu(I). Further additions of CuCl to the neutral species 6a and 7a in a 1:1 ratio resulted in the achievement of the ionic complexes 6b and 7b with ions as counter anions. It was demonstrated that the formation of heterobimetallic or just mononuclear mixed salt complexes was clearly influenced by the polyphosphine arrangement with the tripodal ligands giving the former compounds. However, complexes [M(NP3)Cl]Cl constitute one exception and the type of reaction undergone versus CuCl is a function of the d8 metal centre. 相似文献
17.
Reactions of labile [MCl3(PPh3)2(NCMe)] (M = Tc, Re) precursors with 1H-benzoimidazole-2-thiol (H2L1), 5-methyl-1H-benzoimidazole-2-thiol (H2L2) and 1H-imidazole-2-thiol (H2L3), in the presence of PPh3 and [AsPh4]Cl gave a new series of trigonal bipyramidal M(III) complexes [AsPh4]{[M(PPh3)Cl(H2L1-3)3]Cl3} (M = Re, 1-3; M = Tc, 4-6). The molecular structures of 1 and 3 were determined by X-ray diffraction. When the reactions were carried out with benzothiazole-2-thiol (HL4) and benzoxazole-2-thiol (HL5), neutral paramagnetic monosubstituted M(III) complexes [M(PPh3)2Cl2(L4,5)] (M = Re, 8, 9; M = Tc, 10, 11) were obtained. In these compounds, the central metal ions adopt an octahedral coordination geometry as authenticated by single crystal X-ray diffraction analysis of 8 and 11. Rhenium and technetium complexes 1, 4 and rhenium chelate compounds 8, 9 have been also synthesized by reduction of [MO4]− with PPh3 and HCl in the presence of the appropriate ligand. All the complexes were characterized by elemental analyses, FTIR and NMR spectroscopy. 相似文献
18.
Luigi Busetto Fabio Marchetti Stefano Zacchini Valerio Zanotti 《Inorganica chimica acta》2005,358(4):1204-1216
Acetonitrile is easily displaced from [Fe2{μ-CN(Me)(R)}(μ-CO)(CO)(MeCN)(Cp)2][SO3CF3] (R = 2,6-Me2C6H3 (Xyl) (1a); Me (1b)) upon stirring in THF at room temperature in the presence of [NBu4][SCN]. The resulting complexes trans-[Fe2{μ-CN(Me)(R)}(μ-CO)(CO)(NCS)(Cp)2] (R = Xyl (trans-2a); Me (trans-2b)) are completely isomerised to cis-[Fe2{μ-CN(Me)(R)}(μ-CO)(CO)(NCS)(Cp)2] (R = Xyl (cis-2a); Me (cis-2b)) when heated at reflux temperature. Similarly, the complexes cis-[M2{μ-CN(Me)(R)}(μ-CO)(CO)(NCO)(Cp)2] (M = Fe, R = Me (4a); M = Ru, R = Xyl (4b); M = Ru, R = Me (4c)) and cis-[M2{μ-CN(Me)(R)}(μ-CO)(CO)(N3)(Cp)2] (M = Fe, R = Xyl (5a); M = Fe, R = Me (5b); M = Ru, R = Xyl (5c)) can be obtained by heating at reflux temperature a THF solution of [M2{μ-CN(Me)(R)}(μ-CO)(CO)(MeCN)(Cp)2][SO3CF3] (M = Fe, R = Xyl (1a); M = Fe, Me (1b); M = Ru, R = Xyl (1c); M = Ru, R = Me (1d)) in the presence of NaNCO and NaN3, respectively. The reactions of 5 with MeO2CCCCO2Me, HCCCO2Me and (NC)(H)CC(H)(CN) afford the triazolato complexes [M2{μ-CN(Me)(R)}(μ-CO)(CO){N3C2(CO2Me)2}(Cp)2] (M = Fe, R = Xyl (6a); M = Fe, R = Me (6b); M = Ru, R = Xyl (6c)), [M2{μ-CN(Me)(R)}(μ- CO)(CO){N3C2(H)(CO2Me)}(Cp)2] (M = Fe, R = Me (7a); M = Ru, R = Xyl (7b)) and [Fe2{μ-CN(Me)(Xyl)}(μ-CO)(CO){N3C2(H)(CN)}(Cp)2] (8), respectively. The asymmetrically substituted triazolato complexes 7-8 are obtained as mixtures of N(1) and N(2) bonded isomers, whereas 6 exists only in the N(2) form. Methylation of 6-8 results in the formation of the triazole complexes [Fe2{μ-CN(Me)(Xyl)}(μ-CO)(CO){N3(Me)C2(CO2Me)2}(Cp)2][CF3SO3] (9), [M2{μ-CN(Me)(R)}(μ-CO)(CO){N3(Me)C2(H)(CO2Me)}(Cp)2][CF3SO3] (M = Fe, R = Me (10a); M = Ru, R = Xyl (10b)) and [Fe2{μ-CN(Me)(Xyl)}(μ-CO)(CO){N3(Me)C2(H)(CN)}(Cp)2][CF3SO3], 11. The crystal structures of trans-2b, 4b · CH2Cl2, 5a, 6b · 0.5CH2Cl2 and 8 · CH2Cl2 have been determined. 相似文献
19.
Zdeněk Trávní?ek Igor Popa Radek Zbo?il Ji?í Mikulík 《Journal of inorganic biochemistry》2010,104(4):405-11728
The first FeIII complexes 1-6 with cyclin-dependent kinase (CDK) inhibitors of the type [Fe(Ln)Cl3]·nH2O (n = 0 for 1, 1 for 2, 2 for 3-6; L1-L6 = C2- and phenyl-substituted CDK inhibitors derived from 6-benzylamino-9-isopropylpurine), have been synthesized and characterized by elemental analysis, IR, 57Fe Mössbauer, 1H and 13C NMR, and ES+ mass spectroscopies, conductivity and magnetic susceptibility measurements, and thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC). The study revealed that the compounds are mononuclear, tetrahedral high-spin (S = 5/2) FeIII complexes with an admixture of an S = 3/2 spin state originating probably from five-coordinated FeIII ions either connecting with a bidentate coordination mode of the CDK inhibitor ligand or relating to the possibility that one crystal water molecule enters the coordination sphere of the central atom in a portion of molecules of the appropriate complex. Nearly spin-only value of the effective magnetic moment (5.82 μeff/μB) was determined for compound 1 due to absence of crystal water molecule(s) in the structure of the complex. Based on NMR data and DFT calculations, we assume that the appropriate organic ligand is coordinated to the FeIII ion through the N7 atom of a purine moiety. The cytotoxicity of the complexes was tested in vitro against selected human cancer cell lines (G-361, HOS, K-562 and MCF-7) along with the ability to inhibit the CDK2/cyclinE kinase. The best cytotoxicity (IC50: 4-23 μM) and inhibition activity (IC50: 0.02-0.09 μM) results have been achieved in the case of complexes 2-4, and complexes 3, 4 and 6, respectively. In addition, the X-ray structure of 2-chloro-6-benzylamino-9-isopropylpurine, i.e. a precursor for the preparation of L1, L4 and L5, is also described. 相似文献
20.
M. Cristina Cassani 《Inorganica chimica acta》2005,358(5):1595-1604
The preparation of a series of 1,2-phenylenedioxoborylcyclopentadienyl-metal complexes is described. These are of formula [M{η5-C5H4(BX)}Cl3] [M = Ti and X = CAT (2a), CATt (2b) or CATtt (2c); X = CATtt and M = Zr (4a) or Hf (4b)], [M{η5-C5H4(BX)}2Cl2] [M = Zr, X = CAT (3a) or CATt (3c); or M = Hf, X = CAT (3b) or CATt (3d)], [M{(μ-η5-C5H3BCAT)2 SiMe2}Cl2] [M = Zr (5a) or Hf (5b)], [M{η5-C5H3(BCAT)2}Cl3] [M = Zr (6a) or Hf (6b)], [M{η5-C5H4BCAT}3(THF)] [M = La (7a), Ce (7b) or Yb (7c)], [Sn{η5-C5 H4(BCATt)}Cl](8) and [Fe{η5-C5H4(BCATt)}2] (9). The abbreviations refer to BO2C6H4-1,2 (BCAT) and the 4-But (BCATt) and the (BCATtt) analogues. The compounds 2a-9 have been characterised by microanalysis, multinuclear NMR and mass spectra. The single crystal X-ray structure of the lanthanum compound 7a is presented. 相似文献