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1.
The synthesis and characterization of several complexes of the composition [{M(terpy)}n(L)](ClO4)m (M = Pt, Pd; L = 1-methylimidazole, 1-methyltetrazole, 1-methyltetrazolate; terpy = 2,2′:6′,2″-terpyridine; n = 1, 2; m = 1, 2, 3) is reported and their applicability in terms of a metal-mediated base pair investigated. Reaction of [M(terpy)(H2O)]2+ with 1-methylimidazole leads to [M(terpy)(1-methylimidazole)](ClO4)2 (1: M = Pt; 2: M = Pd). The analogous reaction of [Pt(terpy)(H2O)]2+ with 1-methyltetrazole leads to the organometallic compound [Pt(terpy)(1-methyltetrazolate)]ClO4 (3) in which the aromatic tetrazole proton has been substituted by the platinum moiety. For both platinum(II) and palladium(II), doubly metalated complexes [{M(terpy)}2(1-methyltetrazolate)](ClO4)3 (4: M = Pt; 5: M = Pd) can also be obtained depending on the reaction conditions. In the latter two compounds, the [M(terpy)]2+ moieties are coordinated via C5 and N4. X-ray crystal structures of 1, 2, and 3 are reported. In addition, DFT calculations have been carried out to determine the energy difference between fully planar [Pd(mterpy)(L)]2+ complexes Ip-IVp (mterpy = 4′-methyl-2,2′:6′,2″-terpyridine; L = 1-methylimidazole-N3 (I), 1-methyl-1,2,4-triazole-N4 (II), 1-methyltetrazole-N3 (III), or 3-methylpyridine-N1 (IV)) and the respective geometry-optimized structures Io-IVo. Whereas this energy difference is larger than 70 kJ mol−1 for compounds I, II, and IV, it amounts to only 0.8 kJ mol−1 for the tetrazole-containing complex III, which is stabilized by two intramolecular C-H?N hydrogen bonds. Of all complexes under investigation, only the terpyridine-metal ion-tetrazole system with N3-coordinated tetrazole appears to be suited for an application in terms of a metal-mediated base pair in a metal-modified oligonucleotide. 相似文献
2.
Dimethyl platinum(II) complexes [PtMe2(NN)] {NN = bu2bpy (4,4′-di-tert-butyl-2,2′-bipyridine) (1a), bpy (2,2′-bipyridine) (1b), phen (1,10-phenanthroline) (1c)} reacted with commercial 3-bromo-1-propanol in the presence of 1,3-propylene oxide to afford cis, trans- [PtBrMe2{(CH2)3OH}(NN)] (NN = bu2bpy (2a), bpy (2b), phen (2c)). On the other hand, [PtMe2(NN)] (1a)-(1b) reacted with the trace of HBr in commercial 3-bromo-1-propanol to give [PtBr2(NN)] (NN = bu2bpy (3a), bpy (3b)). The reaction pathways were monitored by 1H NMR at various temperatures. Treatment of 1a-1b with a large excess of 3-bromo-1-propanol at −80 °C gave the corresponding methyl(hydrido)platinum(IV) complexes [PtBr(H)Me2(NN)] (NN = bu2bpy (4a), bpy (4b)) via the oxidative addition of dimethyl platinum(II) complexes with HBr. The complexes [PtBr(H)Me2(NN)] decomposed by reductive elimination of methane above −20 °C for bu2bpy and from −20 to 0 °C for bpy analogue to give methane and platinum(II) complexes [PtBrMe(NN)] (5a)-(5b) and then decomposed at about 0 °C to yield [PtBr2(NN)] and methane. When the reactions were performed at a molar ratio of Pt:RX/1:10, the corresponding complexes [PtBrMe(NN)] (5a)-(5b) were also obtained. The crystal structure of the complex 3b shows that platinum adopts square planar geometry with a twofold axis through the platinum atom. The Pt…Pt distance (5.164 Å) is considerably larger than the interplanar spacing (3.400 Å) and there is no platinum-platinum interaction. 相似文献
3.
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
4.
In the presence of sodium nitrite, the reaction of methyl anthranilate and 2-aminopyridine or o-aminobenzoic acid gives two triazenes, 1-[(2-carboxymethyl)benzene]-3-[2-pyridine]triazene (HL) and 1-[(2-carboxymethyl)benzene]-3-[o-aminobenzoic acid]triazene (H2L′), respectively. In the presence of Et3N, the reaction of Pt(PPh3)2Cl2 and HL or H2L′ produces two triazenido platinum(II) complexes, Pt(PPh3)2(L)Cl (1) and Pt(PPh3)2(L′) (2), respectively, which have been characterized by X-ray crystallography, 31P NMR spectra, UV-Vis spectra, emission spectra and cyclic voltammetry. When excited at 310 nm, complexes 1 and 2 show luminescence at 432 and 442 nm, respectively, which is consistent with the trend of the lowest-energy absorption wavelengths of 1 (376 nm) and 2 (379 nm). Complexes 1 and 2 exhibit one or two redox waves and follow the order 1 (0.97 V) → 2 (0.89 and 0.07 V), which is also in accordance with the trend of the lowest-energy absorption spectra of 1 (376 nm) and 2 (379 nm). 相似文献
5.
Kamal Krishna Sarker Atish Dipankar Jana Chittaranjan Sinha 《Inorganica chimica acta》2006,359(2):695-700
The reaction of Cd(OAc)2 · 4H2O and 1-alkyl-2-(arylazo)imidazole [RaaiR′ where R = H (a), Me (b); R′ = Me (1/3/5), Et (2/4/6)] and NH4NCS/NaNCO in methanol in 1:2:2 mole ratio has afforded [Cd(RaaiR′)2(NCS)2] (3, 4) and [Cd(RaaiR′)2(NCO)2] (5, 6) complexes. The complexes are characterized by different physicochemical methods and in one case, the structure was confirmed by single crystal X-ray diffraction study for title compounds. 相似文献
6.
Tobias Rüffer Björn Bräuer Bernhard Walfort Annie K. Powell Lorenzo Sorace 《Inorganica chimica acta》2007,360(12):3777-3784
The new mononuclear bis(oxamato) complex [n-Bu4N]2[Cu(obbo)] (1) (obbo=o-benzyl-bis(oxamato)) has been synthesized as a precursor for trinuclear oxamato-bridged transition metal complexes. Starting from 1 the homotrinuclear complexes [Cu3(obbo)(pmdta)2(NO3)](NO3)·CH2Cl2·H2O (2) and [Cu3(obbo)(tmeda)2(NO3)2(dmf)] (3) have been prepared, where pmdta = N,N,N′,N″,N″-pentamethyldiethylenetriamine, tmeda = N,N,N′,N′-tetramethylethylenediamine and dmf = dimethylformamide. The crystal structures of 1-3 were solved. The magnetic properties of 2 and 3 were studied by susceptibility measurements versus temperature. For the intramolecular J parameter values of −111 cm−1 (2) and −363 cm−1 (3) were obtained. 相似文献
7.
[Pt(L)2(ox)] (1), [Pt(2-OMeL)2(ox)] (2), [Pt(3-OMeL)2(ox)] (3), [Pt(2,3-diOMeL)2(ox)] (4), [Pt(2,4-diOMeL)2(ox)] (5), [Pt(3,4-diOMeL)2(ox)] (6) and [Pt(3,5-diOMeL)2(ox)]·4H2O (7) platinum(II) oxalato (ox) complexes were synthesized using the reaction of potassium bis(oxalato)platinate(II) dihydrate with 2-chloro-N6-(benzyl)-9-isopropyladenine or its benzyl-substituted analogues (nL). The complexes 1-7, which represent the first platinum(II) oxalato complexes involving adenine-based ligands, were fully characterized by various physical methods including multinuclear and two dimensional NMR spectroscopy. A single-crystal X-ray analysis of [Pt(2,4-diOMeL)2(ox)]·2DMF (5·2DMF; DMF = N,N′-dimethylformamide), proved the slightly distorted square-planar geometry in the vicinity of the Pt(II) ion with one bidentate-coordinated oxalate dianion and two adenine derivatives (nL) coordinated to the Pt(II) centre through the N7 atom of an adenine moiety, thereby giving a PtN2O2 donor set. In vitro cytotoxicity of the prepared complexes was tested by an MTT assay against osteosarcoma (HOS) and breast adenocarcinoma (MCF7) human cancer cell lines. The best results were achieved for the complexes 2 and 5 in the case of both cell lines, whose IC50 values equalled 3.6 ± 1.0, and 4.3 ± 2.1 μM (for 2), and 5.4 ± 3.8, and 3.6 ± 2.1 μM (for 5), respectively. The IC50 equals 9.2 ± 1.5 μM against MCF7 cells in the case of 1. The in vitro cytotoxicity of the mentioned complexes significantly exceeded commercially used platinum-based anticancer drugs cisplatin (34.2 ± 6.4 μM and 19.6 ± 4.3 μM) and oxaliplatin (> 50.0 μM for both cancer cell lines). 相似文献
8.
New mixed polypyridyl {NMIP = 2′-(2″-nitro-3″,4″-methylenedioxyphenyl)imidazo-[4′,5′-f][1,10]-phenanthroline, dmb = 4,4′-dimethyl-2,2′-bipyridine, bpy = 2,2′-bipyridine} ruthenium(II) complexes [Ru(dmb)2(NMIP)]2+ (1) and [Ru(bpy)2(NMIP)]2+ (2) have been synthesized and characterized. The binding of these complexes to calf thymus DNA (CT-DNA) has been investigated with spectroscopic methods, viscosity and electrophoresis measurements. The experimental results indicate that both complexes could bind to DNA via partial intercalation from the minor/major groove. In addition, both complexes have been found to promote the single-stranded cleavage of plasmid pBR 322 DNA upon irradiation. Under comparable experimental conditions compared with [Ru(phen)2(NMIP)]2+, during the course of the dialysis at intervals of time, the CD signals of both complexes started from none, increased to the maximum magnitude, then no longer changed, and the activity of effective DNA cleavage dependence upon concentration degree lies in the following order: [Ru(phen)2NMIP]2+ > complex 2 > complex 1. 相似文献
9.
The “amidate-hanging” Pt mononuclear complexes, which can easily bind a second metal ion with the non-coordinated oxygen atoms in the amidate moieties, have been synthesized and characterized by 1H NMR, MS, IR spectroscopy, and single crystal X-ray analysis. Five new complexes with various amidate ligands and co-ligands, cis-[Pt(PVM)2(en)] · 4H2O (1, PVM = pivaloamidate, en = ethylenediamine), cis-[Pt(PVM)2(NH2CH3)2] · H2O (2), cis-[Pt(PVM)2(NH2tBu)2] (3), cis-[Pt(TCM)2(NH3)2] (4, TCM = trichloroacetamidate), and cis-[Pt(BZM)2(NH3)2] (5, BZM = benzamidate), were successfully synthesized by direct base hydrolysis of the corresponding Pt nitrile complexes, cis-[Pt(NCR)2(Am)2]2+ (P1, P2, P3, and P5) (NCR = nitrile, Am = amine). These nitrile complexes were obtained by introducing nitriles into the Pt aqua complexes, cis-[Pt(OH2)2(Am)2](ClO4)2, whereas introduction of trichloronitrile into [Pt(OH2)2(NH3)2](ClO4)2 induced more facilitated water nucleophilic attack to afford [Pt(TCM)(NH(COH)CCl3)(NH3)2](ClO4) (P4). The base treatments of the precursor complexes (P1-5) lead to produce “amidate-hanging” Pt mononuclear complexes (1-5) without geometry isomerization. The 195Pt chemical shifts for 1-5 exhibit subtle differences of the Pt electron densities among them. 相似文献
10.
Mairéad E. Kelly Ralph Kluge Dirk Steinborn Harry Schmidt 《Inorganica chimica acta》2009,362(4):1323-4211
A number of complexes of the types [PtBr2Me2(N?N)] (N?N = 4,4′-di-Me-2,2′-bpy (1); 4,4′-di-t-Bu-2,2′-bpy (2); 2,2′-bpz (3); bpym (4)) and [PtBr2Me2(L)2] (L = H-pz (5); 4-Me-H-pz (6); H-idz (7); H-im (8); H-bim (9); quaz (10)) are reported. Characterization by NMR (1H, 13C and 195Pt), IR and EI-MS is given. In addition, crystal structures of several of these complexes are described. Furthermore, interactions within these structures including intramolecular hydrogen bonding and π-π stacking interactions are reported. The reactivity of selected mononuclear complexes was investigated and yielded two dinuclear complexes [PPh4][(PtBrMe2)2(μ-Br)(μ-pz)2] (11) and [(PtBr2Me2)2(μ-bpym)] (12), respectively. The latter complex is accompanied by a solid-state structure. Finally, the thermal stability of all complexes is reported. 相似文献
11.
Hong-Yan Li Jing Xiong Qiu-Lei Xu Yun-Mei Tao Jing-Lin Zuo 《Inorganica chimica acta》2011,370(1):398-3327
Six complexes (1-6) with the type of [Ru(bpy)2L]X2 (1-3: L = L1-L3, X = Cl−; 4-6: L = L1-L3, X = PF6−) were synthesized based on 2,2′-bipyridine and three 2,2′-bipyridine derivatives L1, L2 and L3 (L1 = 5,5′-dibromo-2,2′-bipyridine, L2 = 5-bromo-5′-carbazolyl-2,2′-bipyridine, L3 = 5,5′-dicarbazolyl-2,2′-bipyridine). The complexes 1-6 were characterized by 1H NMR, MS(ESI) and IR spectra, along with the X-ray crystal structure analysis for 1, 5 and 6. Their photophysical properties and electrochemiluminescence (ECL) properties were investigated in detail. In the UV-Vis absorption spectra, all complexes 1-6 show strong intraligand (π → π∗) transitions and metal-ligand charge transfer (MLCT, dπ (Ru) → π∗) bands. Upon the excitation wavelengths at ∼508 nm, all complexes 1-6 exhibit typical MLCT emission of ruthenium(II) polypyridyl complexes. The introduction of carbazole moieties improves the MLCT absorption and emission intensity. The ruthenium(II) complexes 1-6 exhibit good electrochemiluminescence (ECL) properties in [Ru(bpy)2L]2+/tri-n-propylamine (TPrA) acetonitrile solution and the complexes with PF6− showed higher ECL emission intensity than that of the complexes with Cl− based on the same ligands. 相似文献
12.
Juan Song Lei Gou Qing-Ran Wu Xiao-Le Yang Yi-Qing Shangguan Fa-Xin Dong Gang-Lin Xue 《Inorganica chimica acta》2011,366(1):134-6870
Two novel Zn(II) coordination polymers, [Zn(2-pytpy)(fum)]n·nH2O (1) and [Zn6(4-pytpy)3(mal)4]n·5n(H2O) (2), (2-pytpy = 4′-(4-pyridyl)-2,2′:6′,2″-terpyridine, 4-pytpy = 4′-(4-pyridyl)-4,2′:6′,4″-terpyridine, H2fum = fumaric acid and H2mal = malic acid) have been hydrothermally synthesized and structurally characterized. Notably, in situ ligand reactions occur in the formation of complexes 1 and 2, in which maleic acid is converted into fumaric acid and malic acid, respectively. Complex 1 is a 1D infinite chain structure, which is extended into a supramolecular layer by intermolecular π…π stacking interactions. Complex 2 is a 3D network structure, in which the bidentate-bridging 4-pytpy ligands link the layers based on the tetranuclear Zn(II) subunits to form the (4,10)-connected network. The luminescent properties of 1 and 2 have been investigated with emission spectra and UV-Vis diffuse reflectance spectra in the solid state. Additionally, these two complexes possess great thermal stabilities. 相似文献
13.
Six 2D and 3D supramolecular complexes [Cu(L1)(O2CCH3)2] · H2O (1), [Cu2(L2)2(μ2-O2CCH3)2](BF4)2 (2), [Cu2(L1)2(BDC)(NO3)2] · 0.5H2O (3) [Cu2(L2)2(BDC)(NO3)2] (4), [Cu2(L3)2(BDC)(NO3)2] · 0.5H2O (5) and [Cu2(L2)2(BDC)(H2O)2](BDC) · 8H2O (6) (L1 = 4′-(4-pyridyl)-2,2′:6′,2″-terpyridine, L2 = 4′-(2-pyridyl)-2,2′:6′,2″-terpyridine, L3 = 4′-phenyl-2,2′:6′,2″-terpyridine, BDC = 1,4-benzenedicarboxylate), have been prepared and structurally characterized by X-ray diffraction crystallography. In complexes 1, 3, and 4, 1D channels are formed through C-H?O and C-H?N hydrogen-bonding interactions, and further linked into 3D structure via C-H?O and O-H?O interactions. Complex 2 is a 2D layer constructed from intermolecular C-H?F and π-π stacking interactions. In the structure of 6, the BDC2− ions and solvent water molecules form a novel 2D layer containing left- and right-handed helical chains via hydrogen-bonds, and an unusual discrete water octamer is formed within the layer. In 2, 4, 6 and [Ag2(L2)2](PF6)2 (7) the bonding types of pendent pyridines of L2 depending on the twist about central pyridines are involved in intramolecular (2 and 4), intermolecular (6) or coordination bonds (7) in-twist-order of 5.8°, 3.7°, 28.2° and 38.0°, respectively. Differently, the pendent pyridines of L1 in 1 and 3 form intermolecular hydrogen bonds despite of distinct corresponding twist angles of 25.1° (1) and 42.6°(3). Meanwhile, π-π stacking interactions are present in 1-6 and responsible for the stabilization of these complexes. 相似文献
14.
The facility of aminoalcohol ligand synthesis via ring opening of cyclohexene oxide with polyamines including a piperazine ring is illustrated here with the syntheses and characterization of (2′-hydroxycyclohexyl)piperazine (1), bis(2′-hydroxycyclohexyl)-piperazine (2), 4-{(2″-hydroxycyclohexyl)-2′-aminoethyl)}piperazine (3), 1-(2″-hydroxycyclohexyl)-4-{(2″-hydroxycyclohexyl)-2′-aminoethyl)}piperazine (4), and 1,4-bis[(2″-hydroxycyclohexyl)-3′-aminopropyl]piperazine (5) described, along with an analogue of 4 in which a single -CH2-CH2- alkyl chain replaces the piperazine ring, 1,5-bis[(2′-hydroxycyclohexyl)amine]-3-azapentane (6). The viability of 5 as a hexadentate ligand was established by preparation of its copper(II) complex and subsequent X-ray crystal structure analysis. The complex [Cu(5)](ClO4)2 cation lies in a distorted octahedral environment with the four nitrogen donors in an approximate plane also incorporating the copper (Cu-Ntert 2.058(4) A; Cu-Nsec 2.072(4) A) and the two alcohol groups occupying axial sites with elongated bonds (Cu-O 2.415(3) A). The piperazine ring adopts a ‘butterfly wing’ geometry, whereas the two cyclohexane rings are in chair conformations. Significant bond angle distortions occur around the copper, exacerbated by the axial Jahn-Teller bond length distortion. The ability of the copper(II) complexes of the aminoalcohols to promote DNA cleavage was examined. Complexes of 2, 3 and 5 are effectively inactive whereas 4 is an efficient single strand cleavage promoter; however, the more flexible close analogue of 4, 6, also proved ineffective. Such observations for a closely related series indicate the subtle influences of spectator ligand rigidity and steric congestion on DNA cleavage promotion. 相似文献
15.
Michael W. Cooke 《Inorganica chimica acta》2008,361(8):2259-2269
We herein describe the synthesis and characterization of a series of homoleptic, Ru(II) complexes bearing peripheral carboxylic acid functionality based upon the novel ligand 4′-(4-carboxyphenyl)-4,4″-di-(tert-butyl)tpy (L1), as well as 4′-(4-carboxyphenyl)tpy (L2) and 4′-(carboxy)tpy (L3) (where tpy = 2,2′: 6′,2″-terpyridine). Inspection of the metal-based oxidations (E1/2 = 1.22-1.42 V) indicates an anodic shift (∼0.2 V) for (L3)2Ru2+ (3b) (E1/2 = 1.40 V) relative to (L2)2Ru2+ (2b) (E1/2 = 1.22 V). The metal-based oxidation (E1/2 = 1.22 V) and ligand-based reductions (E1/2 = −1.25 to −1.52 V) of (L1)2Ru2+ (1) are essentially invariant relative to those of the structural analogue 2b (PF6)2, which suggests no significant electronic effect caused by the tert-butyl groups. This is supported by invariance in the metal-to-ligand charge transfer bands in both the electronic absorption (494-489 nm) and emission spectra (654-652 nm). However, contrary to 2b, complex 1 is both very soluble and exhibits a highly porous solid-state structure with internal cavity dimensions of 15 Å × 14 Å due to the preclusion of inter-annular interactions by the bulky tert-butyl substituents. 相似文献
16.
Three new copper(I) complexes with tricyclohexylphosphine (PCy3) and different diimine ligands, [Cu(phen)(PCy3)]BF4 (1) (phen = 1,10′-phennanthroline), [Cu(bpy)(PCy3)2]BF4 (2) (bpy = 2,2′-bipyridine) and [Cu(MeO-CNN)(PCy3)]BF4 (3) (MeO-CNN = 6-(4-methoxyl)phenyl-2,2′-bipyridine), have been synthesized and characterized. X-ray structure reveals that complexes 1 and 3 are three-coordinated with trigonal geometry, while complex 2 adopts distorted tetrahedron geometry. Complexes 1 and 3 exhibit ligand redistribution reactions in chloromethane solution by addition of excess amount of PCy3, in which three-coordinated 1 changes into four-coordinated [Cu(phen)(PCy3)2]+, and 3 leads to form [Cu(PCy3)2]BF4 and CNN-OMe. All the three complexes display yellow 3MLCT emissions in solid state at room temperature with λmax at 558, 564 and 582 nm for 1, 2 and 3, respectively, and red-shift to 605, 628 and 643 nm at 77 K in dichloromethane solution. 相似文献
17.
Kenneth Kam-Wing Lo Terence Kwok-Ming Lee Kenneth Yin Zhang 《Inorganica chimica acta》2006,359(6):1845-1854
We report here the synthesis, characterisation, electrochemical, photophysical and protein-binding properties of four luminescent ruthenium(II) polypyridine indole complexes [Ru(bpy)2(L1)](PF6)2 (1), [Ru(bpy)2(L2)](PF6)2 (2), [Ru(L1)3](PF6)2 (1a), and [Ru(L2)3](PF6)2 (2a) (bpy = 2,2′-bipyridine; L1 = 4-(N-(2-indol-3-ylethyl)amido)-4′-methyl-2,2′-bipyridine; L2 = 4-(N-(6-N-(2-indol-3-ylethyl)hexanamidyl)amido)-4′-methyl-2,2′-bipyridine). Their indole-free counterparts, [Ru(bpy)2(L3)](PF6)2 (3) and [Ru(L3)3](PF6)2 (3a) (L3 = 4-(N-(ethyl)amido)-4′-methyl-2,2′-bipyridine), have also been synthesised for comparison purposes. Cyclic voltammetric studies revealed ruthenium-based oxidation at ca. +1.3 V versus SCE and diimine-based reductions at ca. −1.20 to −2.28 V. The indole moieties of complexes 1, 2, 1a and 2a displayed an irreversible wave at ca. +1.1 V versus SCE. All the ruthenium(II) complexes exhibited intense and long-lived orange-red triplet metal-to-ligand charge-transfer 3MLCT (dπ(Ru) → π*(L1-L3)) luminescence upon visible-light irradiation in fluid solutions at 298 K and in alcohol glass at 77 K. The binding of the indole-containing complexes to bovine serum album (BSA) has been studied by quenching experiments and emission titrations. 相似文献
18.
Muriel A. Fabre 《Inorganica chimica acta》2005,358(7):2384-2394
Several new mononuclear and dinuclear ruthenium(II) complexes - incorporating 2,2′:6′,2″-terpyridine and acetylacetonate as ancillary ligands and phenylcyanamide derivative ligands - of the type [Ru(tpy)(acac)(L)] and [{Ru(tpy)(acac)}2(μ-L′)] (where tpy = 2,2′:6′,2″-terpyridine, acac = acetylacetonate, L = hmbpcyd = 4-(3-hydroxy-3-methylbutynyl)phenylcyanamide anion (2) and epcyd = 4-ethynylphenylcyanamide anion (3) and L′ = bcpda = bis(4-cyanamidophenyl)diacetylene dianion (4) and bcpea = 9,10-bis(4-cyanamidophenylethynyl)anthracene dianion (5)) were synthesized in a stepwise manner starting from [Ru(tpy)(acac)(Ipcyd)] (1), where Ipcyd = 4-iodophenylcyanamide anion. Tetraphenylarsonium salts of the phenylcyanamide derivative ligands were also prepared. The four complexes have been characterized by UV-Vis, IR, ES-MS, electrochemistry and 1H NMR. Mononuclear complexes 2 and 3 were further characterized by 13C NMR. The single crystal X-ray structure of 2 was determined, it crystallized with one molecule of water with empirical formula of C32H31N5O5Ru, in a monoclinic crystal system and space group of P21/n with a = 17.642(5) Å, b = 9.634(2) Å, c = 20.063(7) Å, β = 92.65(3)°, V = 3406(2) Å3 and Z = 4. The structure was refined to a final R factor of 0.040. The Ru(III/II) couple of 1-3 appeared around 0.34 V versus the saturated calomel electrode in dimethylformamide and at a slightly higher potential, around 0.36-0.37 V for 4 and 5. Spectroelectrochemical studies were also performed for 4 and 5, no intervalence transition was observed despite all attempts. 相似文献
19.
The design of multinuclear Pt(II) complexes with novel structural feature is very important in the search for new anticancer agents. In this work, a dinuclear platinum(II) complex [Pt2(DTBPA)Cl2] (II) [DTBPA = (2,2′-(4,11-dimethyl-1,4,8,11-tetraazacyclotetradecane-1,8-diyl)bis(N-(2-(pyridin-2-yl)ethyl)acetamide))] was synthesized via two different methods and characterized by NMR, IR, electrospray mass spectrometry and elemental analysis. It binds to calf thymus DNA (CT-DNA) and induces its conformational changes. Gel electrophoresis data show that complex II leads to a clear decrease of migration rate of the negatively supercoiled band (form I) of supercoiled pUC19 plasmid. The cytotoxic activity of the complex II was tested against human cervical cancer cell line (Hela) and human ovarian carcinoma cell line (Caov-3) and compared with cisplatin. It displays more potent cytotoxicity against Hela cell line than cisplatin at low concentration range. 相似文献
20.
Laura Battan Mario Manassero Alessandro Pasini Mirella Sansoni 《Inorganica chimica acta》2005,358(3):555-564
The interaction of an excess of the title ligands L− with the cis-Pt(phos)2 moieties gives compounds a-bcis-[Pt(L-O)2(phos)2] (a, phos = P(Ph)3; b, phos = 1/2 dppe), in which O- is preferred to S-coordination. Such preference is confirmed by the fact that the same products are obtained by reaction of excess of L− with the previously reported a-d complexes [Pt(L-O,S)(phos)2]+, (c, phos = PPh3, d, phos = 1/2 dppe), for which chelate ring opening occurs with rupture of Pt-S rather than Pt-O bonds. Compound a can be obtained also by oxidative addition of HL to [Pt(PPh3)3]. The Pt-O bonds in compounds a-d are stable towards substitution by Me2SO, pyridine and tetramethylthiourea. Substitution of L’s occurs with N,N′-diethyldithiocarbamate, which forms a very stable chelate with Pt(II). Thiourea and N,N′-dimethylthiourea also react, because they give rise to cyclometallated products [Pt(phos)2(NRC(S)NHR)]+ (R = H, CH3), with one ionised thioamido group, as revealed by an X-ray investigation of [Pt(PPh3)2(NHC(S)NH2)]+. The preference of O versus S coordination, as well as the stability of the Pt-O bonds, are discussed in terms of antisymbiosis. 相似文献