Corrigendum to "Synthesis and Characterization of New Palladium(II) Thiosemicarbazone Complexes and Their Cytotoxic Activity against Various Human Tumor Cell Lines".

[This corrects the article DOI: 10.1155/2013/524701.].

Synthesis and Characterization of New Palladium(II) Thiosemicarbazone Complexes and Their Cytotoxic Activity against Various Human Tumor Cell Lines.

The palladium(II) bis-chelate complexes of the type [Pd(TSC(1-5))2] (6-10), with their corresponding ligands 4-phenyl-1-(acetone)-thiosemicarbazone, HTSC(1) (1), 4-phenyl-1-(2'-chloro-benzaldehyde)-thiosemicarbazone, HTSC(2) (2), 4-phenyl-1-(3'-hydroxy-benzaldehyde)-thiosemicarbazone, HTSC(3) (3), 4-phenyl-1-(2'-naphthaldehyde)-thiosemicarbazone, HTSC(4) (4), and 4-phenyl-1-(1'-nitro-2'-naphthaldehyde)-thiosemicarbazone, HTSC(5) (5), were synthesized and characterized by elemental analysis and spectroscopic techniques (IR and (1)H- and (13)C-NMR). The molecular structure of HTSC(3), HTSC(4), and [Pd(TSC(1))2] (6) have been determined by single crystal X-ray crystallography. Complex 6 shows a square planar geometry with two deprotonated ligands coordinated to Pd(II) through the azomethine nitrogen and thione sulfur atoms in a cis arrangement.

Influence of an internal trifluoromethyl group on the rhodium(II)-catalyzed reactions of vinyldiazocarbonyl compounds.

Incorporation of a trifluoromethyl group into the structure of 4-(alkoxycarbonyl)vinyldiazocarbonyl compounds greatly decreases the tendency of the carbenoid intermediates formed during Rh(II)-catalyzed reactions to undergo intermolecular processes. Instead, they are prone to experience intramolecular [1,5]- and [1,3]-electrocyclizations to produce reactive cyclopropenes and furans, and these are capable of further transformations.

Hünlich base: (re)discovery, synthesis, and structure elucidation after a century.

After almost 100 years, the structure of the product of the reaction between 2,4-diaminotoluene and formaldehyde was elucidated: derivative 3, which we call the Hünlich base, was synthesized on a multigram scale and its enantiomers were easily separated in preparative amounts. Furthermore, transformation of the NH2 groups to the corresponding bis-iodides and bis-azides is presented. The latter was also used for desymmetrization by click chemistry.

Stannylplumbylenes: bonding between tetravalent tin and divalent lead.

Depending on stoichiometry, reactions of the mixed valence Sn(0)/Sn(III) compound Sn(SnAr(3))(2) (1) (Ar = C(6)H(4)(O(i)Pr)(2)-2,6) with the likewise substituted plumbylene PbAr(2) (3) afforded either the homoleptic distannylplumbylene Pb(SnAr(3))(2) (4) or the heteroleptic arylstannylplumbylene Pb(Ar)SnAr(3) (5), a valence isomer of a stannaplumbene.

The Brønsted acid catalyzed, enantioselective vinylogous Mannich reaction.

The first catalytic, enantioselective vinylogous Mannich reaction of acyclic silyl dienolates is reported. A second-generation 2,2'-dihydroxy-1,1'-binaphthyl (BINOL)-based phosphoric acid has been developed and further optimized as an enantioselective organocatalyst. Upon protonation of the imines, chiral contact ion pairs are generated in situ and attacked highly diastereoselectively by the nucleophile.

Synthesis and elastase-inhibiting activity of 2-pyridinyl-isothiazol-3(2H)-one 1,1-dioxides.

The synthesis of a series of new isothiazol-3(2H)-one 1,1-dioxides with halogenated (mostly fluorinated) pyridinyl and pentafluorophenyl substituents at 2-position is reported. These compounds (18-24) became easily accessible from 2-thiocyanato-1-carboxaldehydes and aminopyridines, pentafluoroaniline, respectively, by an isothiazolium cyclization-oxidation route. Compound 21 exhibited an IC(50) value of 3.

A dihydroxidotetracopper(II) framework supported by 4,4'-(adamantane-1,3-diyl)bis(1,2,4-triazole) and benzene-1,3,5-tricarboxylate bridges.

The new bifunctional ligand 4,4'-(adamantane-1,3-diyl)bis(1,2,4-triazole) (tr(2)ad) and benzene-1,3,5-tricarboxylate sustain complementary coordination bridging for the three-dimensional framework of poly[[bis[mu(3)-4,4'-(adamantane-1,3-diyl)bis(1,2,4-triazole)-kappa(3)N(1):N(2):N(1')]bis(mu(4)-benzene-1,3,5-tricarboxylato-kappa(4)O(1):O(1'):O(3):O(5))di-mu(3)-hydroxido-kappa(6)O:O:O-tetracopper(II)] dihydrate], {[Cu(4)(C(9)H(3)O(6))(2)(OH)(2)(C(14)H(18)N(6))(2)].2H(2)O}(n). The net node is a centrosymmetric (mu(3)-OH)(2)Cu(4) cluster [Cu-O = 1.

Cadmium nitrate coordination polymers with substituted pyridazino[4,5-d]pyridazines.

catena-Poly[[aquabis(nitrato-kappa2O,O')cadmium(II)]-mu-1,2,3,6,7,8-hexahydrocinnolino[5,4,3-cde]cinnoline-kappaN1:kappaN6], [Cd(NO3)2(C12H12N4)(H2O)]n, (I), and catena-poly[[[bis(nitrato-kappa2O,O')cadmium(II)]-mu-2,2,7,7-tetramethyl-1,2,3,6,7,8-hexahydrocinnolino[5,4,3-cde]cinnoline-kappaN1:kappaN6] chloroform solvate], {[Cd(NO2)2(C12H12N4)].CHCl3}n, (II), are the first structurally examined cadmium-pyridazine coordination compounds. They possess one-dimensional polymeric structures supported by the bidentate bridging function of the cinnolino[5,4,3-cde]cinnoline ligands, which lie about inversion centres.

Synthesis, characterization, and crystal structures of novel intramolecularly base-stabilized borane derivatives with six- and seven-membered chelate rings.

The reaction of (2-dimethylaminophenyl)alcohols 1-HOX-2-NMe(2)C(6)H(4) [X = CPh(2) (1), X = CCy(2) (2), X = CPh(2)CH(2) (4)] and 1-phenylaminoalkyl-2-dimethylaminobenzene 1-HN(Ph)X-2-NMe(2)C(6)H(4) [X = C(H)Ph (3), C(H)PhCH(2) (5)] with BH(3)(THF) yielded the BH(2) derivatives 1-H(2)BOX-2-NMe(2)C(6)H(4) [X = CPh(2) (6), CCy(2) (7), CPh(2)CH(2) (9)] and 1-H(2)BN(Ph)X-2-NMe(2)C(6)H(4) [X = C(H)Ph (8), C(H)PhCH(2) (10)]. Treatment of 1-H(2)BOCPh(2)-2-NMe(2)C(6)H(4) (6) with acetic acid gave 1-(CH(3)COO)HBOCPh(2)-2-NMe(2)C(6)H(4) (11). Compounds 6-11 were characterized spectroscopically (NMR, IR, MS).

Extended coordination frameworks incorporating heterobimetallic squares.

The molecular structure of aluminium and iron(III) complexes with 3-phenyl and 3-(4-pyridyl) (HL) substituted acetylacetonate ligands is appreciably distorted. For AlL3 and FeL3 this shows that the orientation of the side pyridyl-N donor atoms lone pairs is about 90 and 135 degrees which favours the assembly of heterobimetallic square patterns in Al(Fe)L3 complexes with metal ions. This was employed for the modular construction of semi-regular heterobimetallic networks, in which the pyridyldiketonate ligands bridge pairs of Fe(Al)/Cd(Co) metal ions and support the structure of 1D and 2D coordination polymers.

Fused pyridazines: rigid multidentates for designing and fine-tuning the structure of hybrid organic/inorganic frameworks.

Fused pyridazines (1,2,3,6,7,8-hexahydro-cinnolino[5,4,3-cde]cinnoline, L and its 2,2,7,7-tetramethyl derivative, Me4L) are designed as rigid multidentate ligands for the construction of framework solids. In combination with copper(I) bromide (iodide) they provide excellent structural examples for predictive engineering and the possibilities for further fine-tuning of the framework architectures facilitated by the tetradentate function of the ligands and effective cooperation of organic and inorganic bridges. This study features control over helical structures for (CuX)n chains and homo/heterochiral combination of the helices in the lattice, the design of a range of channelled and tubular CuX networks and the structural significance of ligand shape complementarity.

Self-assembly sodalite-like framework.

The dense packing of shape complementary N-donor molecules dominates the self-assembly of coordination polymers possessing sodalite-like topology and supports nanosize molecular cages.

Conformational flexibility in a triazole nucleoside derivative: 4-cyano-5-cyanomethyl-1-(2,3,5-tri-O-acetyl-beta-D-ribofuranosyl)-1,2,3-triazole.

The crystal-structure determination of the molecular structure of the hydrophobic compound, 4-cyano-5-cyanomethyl-1-(2,3,5-tri-O-acetyl-beta-D-ribofuranosyl)-1,2,3-triazole, C16H17N5O7, provides us with two different conformations of ribofuranosyl moieties [(C2'-exo, C3'-endo) and C2'-exo] with two markedly different N-glycosidic angles. There are two molecules in the asymmetric unit of the crystal and the overall stereochemistry of the molecules are influenced predominantly by weak intramolecular bifurcated and trifurcated hydrogen bonds of the type C-H..

Fluoro-modified chemotactic peptides: fMLF analogues.

A small library of peptide analogues of the chemotactic tripeptide For-Met-Leu-Phe-NH2 modified by substitution of Leu at position 2 by three different fluorinated amino acids varying in content of fluorine, length of the fluorinated side chain, and alkylation degree at the alpha-carbon atom was synthesized. The influence of the fluorine substitution on the biological activity was investigated by measuring the oxidative activity of neutrophils using a luminol-dependent chemiluminescence assay.

Construction of extended networks with a trimeric pyrazole synthon.

A H-bonded pyrazole trimeric motif drives the self-association of bifunctional tetramethyl-4,4'-bipyrazole, yielding highly interpenetrated 3D frameworks and allowing the engineering by design of a novel supramolecular isomer.

Mixed-anion complexes with a bipyrazolyl ligand. A new entry to a realm of three-dimensional five-connected coordination topologies.

Cross-linking of corrugated square grid coordination layers by anionic bridging groups generates five-connected coordination networks; the 3D topologies of mixed-anion cobalt(II) and nickel(II) complexes with a tetramethyl-substituted 4,4'-bipyrazolyl ligand are supported by mu-SO4(2-) functions and exist as neutral or cationic five-connected arrays involving additional terminal (NCS-) or non-coordinated (NO3-, ClO4-) groups.

A mechanistic dehydration study with [2-(13)C]-DIMBOA.

Dehydration of a 2-(13)C-labeled synthetic sample of the natural aglucone 2,4-dihydroxy-7-methoxy-2H-1,4-benzoxazin-3(4H)-one ([2-(13)C]-DIMBOA, 10) using N-ethoxycarbonyltrichloroacetaldimine led to 3-formyl-6-methoxybenzoxazolin-2(3H)-one ((13)C-labeled FMBOA, 11) with complete transfer of the (13)C label into the -CHO group. On the basis of this finding, a mechanism for the dehydration is proposed.

Synthesis and Properties of Lanthanum- Pyrene Complexes-Structure of [(Cp*La) (μ-Cl) (thf)(μ-η :η :η -C H )], the First Complex with a Pyrene Trianion.

Different bonding modes are characteristic for the lanthanum centers of the title compound, a trinuclear lanthanum-pyrene complex in which an arene trianion is present for the first time (see picture for the structure). Thus, La1 and La3 reside in a tetrahedral environment, the La2 center in a distorted trigonal-bipyramidal one.