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PubMed2004

Electrochemical and phosphorescent properties of new Ir(III) complexes coordinated by various bipyridine derivatives.

Four useful polypyridine iridium(III) complexes in the form of [IrCl2L2]+ were prepared and their spectroscopic and electrochemical properties as well as X-ray crystallography were investigated. The ligands used were L = 2,2'-bipyridine, 4,4'-dimethyl-2,2'-bipyridine, 4,4'-diphenyl-2,2'-bipyridine, 1,10-phenanthroline, 4,7-diphenyl-1,10-phenanthroline, and 2,2'-biquinoline. Synthetic methods were developed by a sequential ligand-replacement, which occurred in the reaction vessel using a microwave oven. All complexes showed that LUMOs are based on the pi-system contribution of the polypyridine ligand for [IrCl2(bpy)2]+, [IrCl2(dmbpy)2]+, [IrCl2(dpbpy)2]+, [IrCl2(phen)2]+, [IrCl2(dpphen)2]+ and [IrCl2(bqn)2]+. The HOMOs are also localized on the polypyridine ligand in the iridium complexes. It was found that [IrCl2L2]+ emits intense phosphorescence at room temperature. In particular, the use of dpbpy as ancillary ligands extends the lifetime (660 ns) of the 3(pi-pi*) excited states of Ir(III) polypyridine complexes. The complex [IrCl2(bqn)2]+ with electron acceptor substituents shows a large red-shift to 622 nm. It is noticed that iridium polypyridine complexes show intense emissions at various colors, such as yellow for [IrCl2(dmbpy)2]+ and red for [IrCl2(bqn)2]+ which can be applied to photosensitizers. The spectroscopic and electrochemical details are also reported herein.

Journal Article↗
PubMed2006

Lanthanide complex coordination polyhedron geometry prediction accuracies of ab initio effective core potential calculations.

lanthanide coordination compounds efficiently and accurately is central for the design of new ligands capable of forming stable and highly luminescent complexes. Accordingly, we present in this paper a report on the capability of various ab initio effective core potential calculations in reproducing the coordination polyhedron geometries of lanthanide complexes. Starting with all combinations of HF, B3LYP and MP2(Full) with STO-3G, 3-21G, 6-31G, 6-31G* and 6-31+G basis sets for [Eu(H2O)9]3+ and closing with more manageable calculations for the larger complexes, we computed the fully predicted ab initio geometries for a total of 80 calculations on 52 complexes of Sm(III), Eu(III), Gd(III), Tb(III), Dy(III), Ho(III), Er(III) and Tm(III), the largest containing 164 atoms. Our results indicate that RHF/STO-3G/ECP appears to be the most efficient model chemistry in terms of coordination polyhedron crystallographic geometry predictions from isolated lanthanide complex ion calculations. Moreover, both augmenting the basis set and/or including electron correlation generally enlarged the deviations and aggravated the quality of the predicted coordination polyhedron crystallographic geometry. Our results further indicate that Cosentino et al.'s suggestion of using RHF/3-21G/ECP geometries appears to be indeed a more robust, but not necessarily, more accurate recommendation to be adopted for the general lanthanide complex case. [Figure: see text].

Computer Simulation↗
PubMed2006

(Strept)avidin as host for biotinylated coordination complexes: stability, chiral discrimination, and cooperativity.

Incorporation of a biotinylated ruthenium tris(bipyridine) [Ru(bpy)(2)(Biot-bpy)](2+) (1) in either avidin or streptavidin-(strept)avidin-can be conveniently followed by circular dichroism spectroscopy. To determine the stepwise association constants, cooperativity, and chiral discrimination properties, diastereopure (Lambda and Delta)-1 species were synthesized and incorporated in tetrameric (strept)avidin to afford (Delta-[Ru(bpy)(2)(Biot-bpy)](2+))(x)() subsetavidin, (Lambda-[Ru(bpy)(2)(Biot-bpy)](2+))(x)() subsetavidin, (Delta-[Ru(bpy)(2)(Biot-bpy)](2+))(x)() subsetstreptavidin, and (Lambda-[Ru(bpy)(2)(Biot-bpy)](2+))(x)() subsetstreptavidin (x = 1-4) For these four systems, the overall stability constants are log beta(4) = 28.6, 30.3, 36.2, and 36.4, respectively. Critical analysis of the CD titrations data suggests a strong cooperativity between the first and the second binding event (x = 1, 2) and a pronounced difference in affinity between avidin and streptavidin for the dicationic guest 1 as well as modest enantiodiscrimination properties with avidin as host.

2,2'-Dipyridyl↗
PubMed2005

Transition metal complexes coordinated by an NAD(P)H model compound and their enhanced hydride-donating abilities in the presence of a base.

The ruthenium(II) and rhenium(I) complexes containing an NAD(P)H model compound, 1-benzyl-1,4-dihydronicotinamide (BNAH), as ligand, [Ru(tpy)(bpy)(BNAH)]2+ (1 a) and [Re(bpy)(CO)3(BNAH)]+ (1 b), were quantitatively produced by the reaction of the corresponding metal hydrido complexes with BNA(+) (1-benzylnicotinamidium cation). In the presence of base with pK(a) = 8.9, 1 a and 1 b have much greater reducing power than "free" BNAH. The oxidation potentials of 1 a in the absence and the presence of triethylamine were 0.55 V and -0.04 V, respectively, versus Ag/AgNO(3), whereas that of "free" BNAH was 0.30 V. Spectroscopic results clearly showed that the base extracts a proton from the carbamoyl group on 1 a and 1 b to give the deprotonated BNAH coordinating to the transition-metal complexes [Ru(tpy)(bpy)(BNAH-H+)]+ (3 a) and [Re(bpy)(CO)3(BNAH-H+)] (3 b); this deprotonation underlies the enhancement in reducing ability. The deprotonated forms 3 a and 3 b can efficiently reduce other NAD(P) models to give the corresponding 1,4-dihydro form, resulting in the deprotonated BNA+ being coordinated to the metal complexes [Ru(tpy)(bpy)(BNA(+)-H+)]2+ (2 a) and [Re(bpy)(CO)3(BNA+-H+)]+ (2 b); "free" BNAH and the protonated adducts 1 a and 1 b cannot act in this way. X-ray crystallography was performed on the PF6- salt of 2 a, and showed that the deprotonated nitrogen atom on the carbamoyl group coordinates to the ruthenium(II) metal center with a bond length of 2.086(3) Angstroms. Infrared spectral data suggested that the deprotonated carbamoyl group on the reduced forms 3 a and 3 b is converted to the imido group, and that the oxygen atom coordinates to the metal center.

Hydrogen-Ion Concentration↗
PubMed2003

The first coordination complexes of selenones: a structural comparison with complexes of sulfones.

Reactivity of the two classes of very weak donors R(2)XO(2) (X = S, R = Me (1) and Ph (2); X = Se, R = Me (3) and Ph (4)) have been studied. Coordination properties of sulfones and selenones in solution and in the gas phase have been compared for the first time using a model bidentate metal complex, [Rh(2)(O(2)CCF(3))(4)]. Two coordination modes, bridging mu(2)-O,O' and terminal eta(1)-O, have been detected. These types of binding were realized in two series of sulfone and selenone metal complexes, polymeric mono-adducts [Rh(2)(O(2)CCF(3))(4).(R(2)XO(2))]( infinity ) (X = S, R = Me (1a); R = Ph (2a); X = Se, R = Ph (4a)) and discrete bis-adducts [Rh(2)(O(2)CCF(3))(4).(R(2)XO(2))(2)] (X = S, R = Ph (2b); X = Se, R = Me (3b)). The compositions and structures of new compounds have been confirmed by NMR and IR spectroscopy, chemical analyses, and X-ray diffraction studies. Compounds 3b and 4a are the first crystallographically characterized metal complexes having selenone ligands coordinated to the metal centers. Preparation and X-ray study of analogous metal complexes of sulfone and selenone ligands allow, for the first time, tracking the structural changes induced by metal coordination. In addition, the X-ray structure of dimethyl selenone, Me(2)SeO(2) (3), an analogue of Me(2)SO(2), has been determined. Geometries of coordinated sulfone and selenones ligands have been compared with those of the corresponding "free" molecules.

Journal Article↗
PubMed1986

Interactions of gold coordination complexes with DNA.

The interactions of certain gold(I) and gold(III) complexes with isolated plasmid pBR322 DNA were defined and compared to those of cis-diamminedichloroplatinum(II), CDDP, using an agarose gel electrophoresis assay. Trichloro(pyridine)gold(III) appeared to bind to DNA as evidenced by its ability to produce dose-dependent changes in the electrophoretic mobilities of closed circular, supercoiled, closed circular, relaxed, and open circular plasmid DNAs. These effects suggest that the gold containing complex induces conformational changes in the plasmid as a result of the compound binding to the DNA and the subsequent unwinding of the double helix and shorting of the DNA. Auranofin [(2,3,4,6-tetra-O-acetyl-1-thio-beta-D-glucopyranosato-S)-triethyl phosphine gold(I)] did not appear to interact with DNA under any conditions. However, its analog chloro(triethylphosphine) gold(I) interacted with DNA at pH 9.5 in borate buffer and produced electrophoretic mobility changes in pBR322 DNA which were different from those produced by the gold(III) complexes that were evaluated. Binding of chloro(triethylphosphine) gold(I) was inhibited by the co-addition of the thiosugar portion of auranofin suggesting preferential binding of the gold moiety to thiosugar, which results in the production of auranofin (or a sugar containing) gold complex and inhibition of gold binding to DNA. The interactions of a number of gold compounds with DNA were also evidenced by their abilities to inhibit the binding of ethidium bromide to DNA. The results from these studies indicate that: gold containing complexes can bind to, and produce conformational changes in, DNA; gold(I) and gold(III) complexes may interact with DNA via different chemical mechanisms to produce different conformational changes in DNA; and certain coordinating ligands in gold complexes (e.g. Cl, Br and SCN) can be exchanged for binding sites on DNA by gold.

Animals↗
PubMed2003

Electrochemical and phosphorescent properties of new mixed-ligand Ir(II) complexes coordinated with both terpyridine and various bipyridine derivatives.

Seven useful mixed-ligand complexes in the form of [Ir(terpy)(L)Cl]2+ were prepared and their spectroscopic and electrochemical properties were investigated. The ligands used were terpy = 2,2':6',2''-terpyridine, L = 2,2'-bipyridine, 4,4'-dimethyl-2,2'-bipyridine, 4,4'-diphenyl-2,2'-bipyridine, 1,10-phenanthroline, 5-phenyl-1,10-phenanthroline, 4,7-diphenyl-1,10-phenanthroline, 2,3-bis(2-pyridyl)pyrazine. Synthetic methods were developed by a sequential ligand-replacement which occurred in the reaction vessel using a microwave oven. All complexes showed that LUMOs are based on the pi-system contribution of the terpyridine ligand for [Ir(terpy)(bpy)Cl]2+, [Ir(terpy)(dmbpy)Cl]2+, [Ir(terpy)(dpbpy)Cl]2+, [Ir(terpy)(phen)Cl]2+, [Ir(terpy)(dpphen)Cl]2+ and [Ir(terpy)(phphen)Cl]2+. On the other hand, the LUMO in the [Ir(terpy)(bppz)Cl]2+ complex is localized on the pi-system of the bppz ligand, whereas the HOMOs in the iridium complexes are localized on the terpyridine ligand. It was found that Ir(terpy)(L)Cl emits in a fluid solution at room temperature. The ancillary ligands, such as terpy and bpy, have been explored to extend the lifetime of the triplet 3(pi-pi') excited states of Ir(III) terpyridine complexes. Ir(III) terpyridine units with an electron donor (dmbpy) or electron acceptor substituents (terpy, dpbpy, phphen, dpphen and bppz) are found to decrease the energy of the 3LC states for use as photosensitizer molecular components in supramolecular devices. The spectroscopic and electrochemical details are also reported herein.

Journal Article↗
PubMed2004

WAVE/SCAR, a multifunctional complex coordinating different aspects of neuronal connectivity.

Although it is well established that the WAVE/SCAR complex transduces Rac1 signaling to trigger Arp2/3-dependent actin nucleation, regulatory mechanisms of this complex and its versatile function in the nervous system are poorly understood. Here we show that the Drosophila proteins SCAR, CYFIP and Kette, orthologs of WAVE/SCAR complex components, all show strong accumulation in axons of the central nervous system and indeed form a complex in vivo. Neuronal defects of SCAR, CYFIP and Kette mutants are, despite the initially proposed function of CYFIP and Kette as SCAR silencers, indistinguishable and are as diverse as ectopic midline crossing and nerve branching as well as synapse undergrowth at the larval neuromuscular junction. The common phenotypes of the single mutants are readily explained by the finding that loss of any one of the three proteins leads to degradation of its partners. As a consequence, each mutant is unambiguously to be judged as defective in multiple components of the complex even though each component affects different signaling pathways. Indeed, SCAR-Arp2/3 signaling is known to control axonogenesis whereas CYFIP signaling to the Fragile X Mental Retardation Protein fly ortholog contributes to synapse morphology. Thus, our results identify the Drosophila WAVE/SCAR complex as a multifunctional unit orchestrating different pathways and aspects of neuronal connectivity.

Adaptor Proteins, Signal Transducing↗
PubMed1991

Inactivation of intestinal alkaline phosphatase by inositol hexaphosphate-Cu (II) coordinate complexes.

Alkaline phosphatase (APase) was greater than 99% inactivated upon incubation with myo-inositol hexakisphosphate (IHP) and Cu(II) ions. In the absence of Cu(II), IHP did not inactivate the enzyme. Likewise, cupric ions alone did not produce inactivation. Reactions of APase with IHP plus Cu(II) were competitively inhibited by zinc ions. In contrast to the marked effect of (IHP-Cu) chelate complexes on APase activity, the complexes of IHP with either Zn(II) or Mn(II) had no discernable effect. Both the extent and the rate of activity loss were dependent on the combined IHP and Cu(II) concentration. At an IHP to Cu(II) ratio of 11.6, the extent of inactivation was approximately proportional to the Cu(II) concentration with maximal inactivation attained above 10 microM. Under the same conditions, a nonlinear relation (saturation kinetics) was observed between the pseudo first-order rate constants for the reaction and the IHP and Cu(II) concentration. On the basis of adherence of the data to a mechanism involving an intermediate whose concentration was rate determining, it was suggested that a ternary complexes composed of the apoprotein, the catalytic site zinc ions, and one or more specific IHP-Cu(II) complex [( IHP-Cu]*) may be the first step along the reaction coordinate. Relevant to this possibility which assumes active site interaction is the fact that both IHP alone and (IHP-Cu) complexes are good competitive inhibitors of p-nitrophenyl phosphate hydrolysis under the same solution conditions wherein APase inactivation occurs in the absence of substrate. Rates of enzyme inactivation are decreased with an increase in pH from 6.5 to 8.0. They are also dependent upon buffer type and concentration, apparently related to their association constants for cupric ion binding. Over and above such specific effects, rates of inactivation are also reduced with an increase in ionic strength. Depending on the ratio and concentrations of IHP and Cu(II) used in the reaction with APase, subsequent exposure to EDTA followed by assay in the presence of Zn(II) gave recoveries of activity ranging from 60% to 100%. Both the prior inactivated enzyme (containing IHP and cupric ions) in the presence of EDTA and the native APase upon simultaneous exposure to IHP, Cu(II), and EDTA were slowly and irreversibly inactivated. Correction for this effect gave reconstitution of activity of the (IHP-Cu)-inactivated APase by Zn(II) addition equivalent to that which could be obtained by EDTA-treatment of the native enzyme.(ABSTRACT TRUNCATED AT 400 WORDS)

Alkaline Phosphatase↗
PubMed2003

The MRN complex: coordinating and mediating the response to broken chromosomes.

The MRE11-RAD50-NBS1 (MRN) protein complex has been linked to many DNA metabolic events that involve DNA double-stranded breaks (DSBs). In vertebrate cells, all three components are encoded by essential genes, and hypomorphic mutations in any of the human genes can result in genome-instability syndromes. MRN is one of the first factors to be localized to the DNA lesion, where it might initially have a structural role by tethering together, and therefore stabilizing, broken chromosomes. This suggests that MRN could function as a lesion-specific sensor. As well as binding to DNA, MRN has other roles in both the processing and assembly of large macromolecular complexes (known as foci) that facilitate efficient DSB responses. Recently, a novel mediator protein, mediator of DNA damage checkpoint protein 1 (MDC1), was shown to co-immunoprecipitate with the MRN complex and regulate MRE11 foci formation. However, whether the initial recruitment of MRN to DSBs requires MDC1 is unclear. Here, we focus on recent developments in MRN research and propose a model for how DSBs are sensed and the cellular responses to them are mediated.

Acid Anhydride Hydrolases↗
PubMed2006

Enantioselective intramolecular hydroamination catalyzed by lanthanide ate complexes coordinated by N-substituted (R)-1,1'-binaphthyl-2,2'-diamido ligands.

Ytterbium and lutetium ionic complexes derived from enantiopure substituted (R)-binaphthylamine ligands, of the general formula [Li(THF)n][Ln[(R)-C20H12(NR)2]2], have been investigated for the hydroamination/cyclization of several aminopentenes and an aminohexene. Complexes with isopropyl or cyclohexyl substituents on nitrogen atoms were found to be efficient catalysts under mild conditions for the formation of N-containing heterocycles with enantiomeric excesses up to 78%.

Journal Article↗
PubMedDate not supplied

Coordination complexes of platinum as antitumor agents.

Rosenberg and VanCamp first reported the bacteriostatic and antitumor properties of certain platinum coordination compounds. This pioneering work has led to the synthesis and testing of a large number of related platinum products and the clinical use of cis-dichlorodiammineplatinum (II). This drug has proven very efficacious against a wide variety of mouse tumors when employed as the sole chemotherapeutic agent and has also been combined successfully with other antitumor agents, such as cyclophosphamide and cytosine arabinsoide. Unfortunately, cis-dichlorodiammineplatinum (II) has a low therapeutic index with renal toxicity being the principal limitation of its use. This has prompted the synthesis and testing of many related platinum compounds, of which cis-dichlorobiscyclopentylamine-platinum (II) and the "platinum blues" appear most promising. Experience in the synthesis, purification, and testing of such products will be discussed together with identification of outstanding unsolved problems in this area.

Animals↗
PubMed2001

Bis(triethanolamine)cadmium(II) and -mercury(II) saccharinates: seven-coordinate complexes containing both tri- and tetradentate triethanolamine ligands.

The structures of the title triethanolamine (tea) complexes of Cd(II) and Hg(II) saccharinates, bis(triethanolamine)-kappa3O,N,O';kappa4O,N,O',O"-cadmium(II) 1,2-benzisothiazol-3(2H)-onate 1,1-dioxide, [Cd(C6H15NO3)2](C7H4NO3S)2, (I), and bis(triethanolamine)-kappa3O,N,O';kappa4O,N,O',O"-mercury(II) 1,2-benzisothiazol-3(2H)-onate 1,1-dioxide, [Hg(C6H15NO3)2](C7H4NO3S)2, (II), or [M(tea)2](sac)2, where M is Cd(II) or Hg(II) and sac is the saccharinate anion, reveal seven-coordinate metal ions in both complexes. Both complex cations, [M(tea)2]2+, adopt a monocapped trigonal prism geometry in which the two tea ligands exhibit different coordination modes to achieve seven-coordination. One tea ligand acts as a tetradentate ligand using all its donor atoms, while the other behaves as a tridentate O,N,O'-donor ligand, with one of its ethanol groups remaining uncoordinated. The H atoms of the free and coordinated hydroxyl groups of the tea ligands are involved in hydrogen bonding with the amine N atom, and with the carbonyl and sulfonyl O atoms of neighbouring sac ions, forming an infinite three-dimensional network. A weak pi-pi interaction between the phenyl rings of the sac ions also occurs.

Journal Article↗
PubMed1994

Effects of substitution of proposed Zn(II) ligand His81 or His64 in phage T4 gene 32 protein: spectroscopic evidence for a novel zinc coordination complex.

T4 gene 32 protein (gp32), the prototype helix-destabilizing or single-stranded (ss) DNA binding protein, contains one tightly coordinated Zn2+ ion bound tetrahedrally by three cysteines (residues 77, 87, and 90) and a fourth non-thiol donor. In previous work, it was shown that the proposed non-thiol ligand His81 could be readily substituted with nonliganding glutamine and alanine residues without deleterious effects on gp32 structure and simple assays of ssDNA binding. In this paper we show that exchange broadening of bulk 35Cl- anion by protein-bound Zn(II) is not observed in the His81-->Ala (H81A) mutant, unless the coordination site is disrupted with an organomercurial, p-mercuriphenylsulfonate. This suggests that, in the mutant protein, anions, and by implication solvent molecules, do not gain access to a newly formed inner shell Zn(II) coordination site as a result of mutagenesis. H81A gp32 is characterized by nearly wild-type helix-destabilizing activity on poly(d[A-T]) and highly cooperative binding to the polynucleotide poly(A) at pH 7.7 over the temperature range from 20 to 42 degrees C at 0.35 M NaCl, exhibiting only a approximately 2.5-4-fold decrease in poly(A) affinity. Limited proteolysis experiments show that an additional tryptic cleavage site maps to the Arg111-Lys112 bond within the protease-resistant core domain of the H81A gp32 following long incubation times and results in the accumulation of a 16-kDa subcore fragment. This new cleavage site is within the internal LAST motif, which has been proposed to be directly involved in cooperative ssDNA binding [Casas-Finet, J. R., & Karpel, R. L. (1993) Biochemistry 32, 9735-9744]. Thus substitution of His81 with Ala subtly alters the conformation or dynamics of the backbone around the LAST motif, which may be manifest as a moderately lower cooperative binding affinity of H81A gp32 for polynucleotides. H81A gp32, however, is fully functional in stimulating in vitro homologous pairing catalyzed by the T4 recombinase uvsX protein. Since substitution of His81 with a nonliganding Ala is nearly silent, we propose an alternative mode of Zn(II) coordination in T4 gene 32 protein, involving His64 rather than His81 as the fourth non-thiol ligand. That replacement of His64, and not His81, with Cys results in marked changes in the first coordination sphere of ligands as evidenced by the optical spectrum of Co(II)-substituted H64C gp32 is consistent with the noninvolvement of His81 and implicates a novel His64-X12-Cys77-X9-Cys87-X2-Cys90 coordination motif, unique among zinc-containing nucleic acid binding proteins.

Adenosine Triphosphatases↗
PubMed2005

Lanthanide complexes coordinated by N-substituted (R)-1,1'-binaphthyl-2,2'-diamido ligands in the catalysis of enantioselective intramolecular hydroamination.

A new family of lanthanide ionic complexes derived from chiral, substituted (R)-binaphthylamine ligands, [Li(thf)(4)][Ln{(R)-C(20)H(12)(NR)(2)}(2)] (Ln=Yb, Sm, Nd, or Lu), has been synthesized and characterized by X-ray crystal structure analyses. All complexes have been tested as new catalysts for the hydroamination/cyclization of 1-(aminomethyl)-1-allylcyclohexane. Ytterbium complexes proved to be both the most active and the most enantioselective, and the use of the complex [Li(thf)(4)][Yb{(R)-C(20)H(12)(NC(3)H(7))(2)}(2)], bearing isopropyl radicals on the nitrogen atoms, allowed the formation of the corresponding spiropyrrolidine in high yield with up to 70 % ee.

Amides↗
PubMed1997

Cobalt as a Probe for Zinc in Metalloenzyme Model Compounds? A Comparison of Spectroscopic Features and Coordination Geometry of Four- and Five-Coordinate Complexes. Crystal and Molecular Structures of [Co(eta(3)-Tp(Ph))(eta(2)-Tp(Ph))], [(eta(3)-Tp(Ph))Zn(anthranilate)], and [(eta(3)-Tp(Ph))M(eta(2)-acac)] (Tp(Ph) = Hydrotris(3-phenylpyrazol-1-yl)borate, acac = Pentane-2,4-dionate, and M = Zn, Co).

The reaction of cobalt(II) perchlorate with 1 equiv each of potassium hydroxide and potassium hydrotris(3-phenylpyrazolyl)borate (KTp(Ph)) leads to the formation of the blood-red bis(ligand) complex [Co(eta(3)-Tp(Ph))(eta(2)-Tp(Ph))]. This compound crystallizes in the monoclinic space group P2(1)/n, with a = 10.690(5) Å, b = 34.243(15) Å, c = 12.923(4) Å, beta = 96.17(3) degrees, Z = 4, V = 4703(3) Å(3), and R = 0.040. The molecular structure contains a square CoN(5) pyramid with an agostic BH.Co interaction of 2.17(2) Å. One Tp(Ph) ligand acts tridentate; the other, bidentate. The reaction of KTp(Ph) with zinc and cobalt halides yields a series of heteroleptic halogeno complexes [(Tp(Ph))MX]. The zinc species are all tetrahedral, while in the case of cobalt(II) the UV-vis spectra indicate an equilibrium of tetra- and pentacoordinated species depending on the anion size and the donor properties of the solvent. Metathesis reactions with carboxylates yield mononuclear complexes [(Tp(Ph))M(O(2)CR)]; M = Zn(II), Co(II); RCO(2)(-) = acetate, benzoate, 4-fluorobenzoate, and 4-nitrobenzoate. The infrared bands nu(as)(CO(2)) and nu(sym)(CO(2)) indicate monodentate carboxylate ligands in the zinc complexes in the solid state and in solution. The cobalt complexes [(Tp(Ph))Co(carboxylate)] are dark blue in dichloromethane and in the solid state when grown from dichloromethane solution. Tetrahydrofuran solutions and crystals grown from tetrahydrofuran are pink, purple, or reddish violet. The 2-aminobenzoate (anthranilate) complexes [(Th(Ph))M(anthranilate)], M = Zn(II), Co(II), have been prepared. [(eta(3)-Tp(Ph))Zn(anthranilate)] crystallizes in the monoclinic space group P2(1)/n, with a = 13.205(4) Å, b = 15.643(3) Å, c = 15.116(3) Å, beta = 98.86(2) degrees, Z = 4, V = 3085(1) Å(3), and R = 0.034. Anthranilate acts as a chelating oxygen ligand with Zn-O distances of 1.932(2) and 2.460(2) Å. The amino group is not involved in metal coordination. The reaction of the chloro complexes [(Tp(Ph))MCl] with sodium or potassium acetylacetonate leads to isotypic zinc and cobalt complexes [(eta(3)-Tp(Ph))M(eta(2)-acac)]. Both crystallize in the monoclinic space group P2(1)/c, with Z = 4, the zinc compound with a = 16.334(3) Å, b = 11.545(2) Å, c = 15.816(3) Å, beta = 94.77(1) degrees, V = 2972(1) Å(3), and R = 0.039 and the cobalt compound with a = 16.358(7) Å, b = 11.519(2) Å, c = 15.847(6) Å, beta = 95.30(3) degrees, V = 2973(2) Å(3), and R = 0.035. The structures are best described as slightly distorted trigonal bipyramids with the two axial positions occupied by one of the acetylacetonate O and one of the tripodal N donor atoms. Ligand profiles of Tp(Ph) and related ligands have been calculated to visualize the angular encumbrance of the ligands.

Journal Article↗
PubMed2006

Gold coordination complexes as anticancer agents.

Metal ions are known to bind with nucleic acids and thereby alter their conformation and biological function. The metal ion-base interaction depends on the nature of both metal and bases; a certain site of coordination is preferred. One of the most notable successes for inorganic drugs has been the effectiveness of platinum complexes against cancer. These advances have spurred a surge of investigations to identify new inorganic agents for use in chemotherapy with improved specificity and decreased toxic side effects. Gold(I) and gold(III) complexes, the last isostructural and isoelectronic with platinum(II) complexes, are potentially attractive as anticancer agents. The design of an effective anticancer agent is a complicated game that must encompass not only the drug's inherent inhibitory properties but also its delivery, dosage, and residence time in vivo. Gold(I) and gold(III) complexes overcome some of these challenges by forming strong covalent attachments to targets. Au(III) isoelectronic with Pt(I1)-d8 system usually forms square planar complexes in solution. Since the square planar geometry of Pt(II) is important for its action as an anticancer drug, Au(III) compounds also can be used for the same purpose with the added advantage of decreased toxicity. This, together with the recent finding that certain transitional metal complexes like Au and Pt complexes have been found to be potentially useful in cancer chemotherapy, created a renewed interest in the study of the interactions of metal ions with respect to the site of binding and the structure and stability of the complexes. This work was motivated by the thought that information on the variety of Au(III) complexes and their effects can be obtained by studying the properties of Au complexes with various ligands. Various studies in the past have shown that Au complexes are very attractive in view of their application as anticancer agents.

Antineoplastic Agents↗