Iridium Complexes with BIAN-Type Ligands: Synthesis, Structure and Redox Chemistry.

A series of iridium complexes with bis(diisopropylphenyl)iminoacenaphtene (dpp-bian) ligands, [Ir(cod)(dpp-bian)Cl] (), [Ir(cod)(NO)(dpp-bian)](BF) () and [Ir(cod)(dpp-bian)](BF) (), were prepared and characterized by spectroscopic techniques, elemental analysis, X-ray diffraction analysis and cyclic voltammetry (CV). The structures of - feature a square planar backbone consisting of two C = C π-bonds of 1,5-cyclooctadiene (cod) and two nitrogen atoms of dpp-bian supplemented with a chloride ion (for ) or a NO group (for ) to complete a square-pyramidal geometry. In the nitrosyl complex , the Ir-N-O group has a bent geometry (the angle is 125°).

Effects of Bis(imino)acenaphthene (Bian)-Derived Ligands on the Cytotoxicity, DNA Interactions, and Redox Activity of Palladium(II) Bipyridine Complexes.

A series of heteroleptic bipyridine Pd(II) complexes based on 1,2-bis[(2,6-diisopropylphenyl)imino]acenaphthene (dpp-Bian) or 1,2-bis[(2,4,6-trimethylphenyl)imino]acenaphthene (tmp-Bian) were prepared. All complexes were fully characterized by spectrochemical methods, and their crystal structures were confirmed by X-ray diffraction analysis. The 72 h stability of heteroleptic bipyridine Pd(II) complexes with Bian ligands under physiological conditions was investigated using H NMR spectroscopy.

Trapping of Ag into a Perfect Six-Coordinated Environment: Structural Analysis, Quantum Chemical Calculations and Electrochemistry.

Self-assembly of (BuN)[β-MoO], AgNO, and 2-bis[(2,6-diisopropylphenyl)-imino]acenaphthene (dpp-bian) in DMF solution resulted in the (BuN)[β-{Ag(dpp-bian)}MoO] () complex. The complex was characterized by single crystal X-ray diffraction (SCXRD), X-ray powder diffraction (XRPD), diffuse reflectance (DR), infrared spectroscopy (IR), and elemental analysis. Comprehensive SCXRD studies of the crystal structure show the presence of Ag in an uncommon coordination environment without a clear preference for Ag-N over Ag-O bonding.

Coordination of Pt(IV) by {PW} Macrocyclic Inorganic Cavitand: Structural, Solution, and Electrochemical Studies.

Hydrothermal reaction of a macrocyclic inorganic POM cavitand Li(NH)H[PWO] with [Pt(HO)(OH)] results in coordination of up to six {Pt(HO)(OH)} fragments to the internal surface of the polyoxoanion. The product was isolated as K(NH)H[{Pt(OH)(HO)}PWO]·79HO () and characterized by multiple techniques in the solid state (SCXRD, XRPD, XPS, FTIR, and TGA) and in solution (NMR, ESI-MS, and HPLC-ICP-AES). Electrochemical properties were studied both in solution and as components of the paste electrode.

Novel Copper(II) Complexes with Dipinodiazafluorene Ligands: Synthesis, Structure, Magnetic and Catalytic Properties.

The reactions of CuX (X = Cl, Br) with dipinodiazafluorenes yielded four new complexes [CuXL] (X = Cl (), Br (), L = (1R,3R,8R,10R)-2,2,9,9-Tetramethyl-3,4,7,8,9,10-hexahydro-1H-1,3:8,10-dimethanocyclopenta [1,2-b:5,4-b']diquinolin-12(2H)-one) and [(CuX)L]n (X = Cl (), Br (), L = (1R,3R,8R,10R,1'R,3'R,8'R,10'R)-2,2,2',2',9,9,9',9'-Octamethyl-1,1',2,2',3,3',4,4',7,7',8,8',9,9',10,10'-hexadecahydro-1,3:1',3':8,10:8',10'-tetramethano-12,12'-bi(cyclopenta [1,2-b:5,4-b']diquinolinylidene). The complexes were characterized by IR and EPR spectroscopy, HR-ESI-MS and elemental analysis. The crystal structures of compounds , and were determined by X-ray diffraction (XRD) analysis.

Heteroleptic Pd(II) and Pt(II) Complexes with Redox-Active Ligands: Synthesis, Structure, and Multimodal Anticancer Mechanism.

A series of heteroleptic square-planar Pt and Pd complexes with bis(diisopropylphenyl) iminoacenaphtene (dpp-Bian) and Cl, 1,3-dithia-2-thione-4,5-dithiolate (dmit), or 1,3-dithia-2-thione-4,5-diselenolate (dsit) ligands have been prepared and characterized by spectroscopic techniques, elemental analysis, X-ray diffraction analysis, and cyclic voltammetry (CV). The intermolecular noncovalent interactions in the crystal structures were assessed by density functional theory (DFT) calculations. The anticancer activity of Pd complexes in breast cancer cell lines was limited by their solubility.

Novel Oxidovanadium Complexes with Redox-Active R-Mian and R-Bian Ligands: Synthesis, Structure, Redox and Catalytic Properties.

A new monoiminoacenaphthenone 3,5-(CF)CH-mian (complex ) was synthesized and further exploited, along with the already known monoiminoacenaphthenone dpp-mian, to obtain oxidovanadium(IV) complexes [VOCl(dpp-mian)(CHCN)] () and [VOCl(3,5-(CF)CH-bian)(HO)][VOCl(3,5-(CF)CH-bian)]·2.85DME () from [VOCl(CHCN)(HO)] () or [VCl(THF)]. The structure of all compounds was determined using X-ray structural analysis.

Intramolecular aurophilic interactions in dinuclear gold(I) complexes with twisted bridging 2,2'-bipyridine ligands.

Elimination of the chloride ion from the [(PPh)AuCl] complex using silver triflate (AgOTf) in the presence of 2,2'-bipyridine Rbpy (the Au : Rbpy molar ratio is 2 : 1) in dichloromethane at room temperature leads to dinuclear gold(I) complexes [(PPhAu)(μ-Rbpy)](OTf) (Rbpy = bpy (1), dbbpy (2), CHObpy (3), 3-COCHbpy (4), 4-COCHbpy (5)) in high yields. The crystal structures for all compounds were determined using X-ray diffraction analysis. In all structures, gold ions are in a typical linear environment, and the bipyridine molecule is twisted, which allows intramolecular aurophilic interactions.

Keggin-type polyoxometalate 1 : 1 complexes of Pb(II) and Bi(III): experimental, theoretical and luminescence studies.

Bi3+ and Pb2+ uptake by a monolacunary Keggin-type [PW11O39]7- anion leads to the formation of [PW11O39Bi]4- and [PW11O39Pb]5- complexes with a stereochemically active lone pair at the incorporated heterometal. The two complexes were isolated as (TBA)4[PW11O39Bi] (1) and (TBA)5[PW11O39Pb] (2) and characterized by 31P and 183W NMR spectroscopy, high-resolution electrospray mass-spectrometry (HR-ESI-MS) and cyclic voltammetry (CV). EXAFS and XANES data confirm the unchanged oxidation state and ψ-square pyramidal geometry of Bi3+ and Pb2+ in 1 and 2.

Hydrolysis of Element (White) Phosphorus under the Action of Heterometallic Cubane-Type Cluster {MoPdS}.

Reaction of heterometallic cubane-type cluster complexes-[Mo{Pd(dba)}SCl(dbbpy)]PF, [Mo{Pd(tu)}SCl(dbbpy)]Cl and [Mo{Pd(dba)}S(acac)(py)]PF, where dba-dibenzylideneacetone, dbbpy-4,4'-di--butyl-2,2'-bipyridine, tu-thiourea, acac-acetylacetonate, py-pyridine, with white phosphorus (P) in the presence of water leads to the formation of phosphorous acid HPO as the major product. The crucial role of the Pd atom in the cluster core {MoPdS} has been established in the hydrolytic activation of P molecule. The main intermediate of the process, the cluster complex [Mo{PdP(OH)}SCl(dbbpy)] with coordinated P(OH) molecule and phosphine PH, have been detected by P NMR spectroscopy in the reaction mixture.

A Sterically Hindered Derivative of 2,1,3-Benzotelluradiazole: A Way to the First Structurally Characterised Monomeric Tellurium-Nitrogen Radical Anion.

Interaction of the tetradentate redox-active 6,6'-[1,2-phenylenebis(azanediyl)]bis(2,4-di-tert-butylphenol) (H L) with TeCl leads to neutral diamagnetic compound TeL (1) in high yield. The molecule of 1 has a nearly planar TeN O fragment, which suggests the formulation of 1 as Te L , in agreement with the results of DFT calculations and QTAIM and NBO analyses. Reduction of 1 with one equivalent of [CoCp ] leads to quantitative formation of the paramagnetic salt [CoCp ] [1] , which was characterised by single-crystal XRD.

Arene-Ruthenium(II) Complexes Containing 11-Indeno[1,2-]quinoxalin-11-one Derivatives and Tryptanthrin-6-oxime: Synthesis, Characterization, Cytotoxicity, and Catalytic Transfer Hydrogenation of Aryl Ketones.

A series of novel mono- and binuclear arene-ruthenium(II) complexes [(-cym)Ru(L)Cl] containing 11-indeno[1,2-]quinoxalin-11-one derivatives or tryptanthrin-6-oxime were synthesized and characterized by X-ray crystallography, IR, NMR spectroscopy, cyclic voltammetry, and elemental analysis. Theoretical calculations invoking singlet state geometry optimization, solvation effects, and noncovalent interactions were done using density functional theory (DFT). DFT calculations were also applied to evaluate the electronic properties, and time-dependent DFT was applied to clarify experimental UV-vis results.

Highly cytotoxic gold(i)-phosphane dithiocarbamate complexes trigger an ER stress-dependent immune response in ovarian cancer cells.

Ovarian cancer is a highly aggressive disease which is treated by surgery and platinum chemotherapy. However, a significant proportion of treated patients develop resistance to platinum treatment resulting in tumor relapse. Acquired platinum resistance has been recently correlated with activation of pro-survival endoplasmic reticulum (ER) stress responses.

Easy Ligand Activation in the Coordination Sphere of Ru inside the [PWO] Backbone.

Irradiation of the Keggin-type [PWO{Ru(NO)}] () polyoxometalate in CHCN results in rapid NO ligand elimination with the formation of [PWO{Ru(CHCN)}] (). This complex offers an easy entry into the Ru-based chemistry of the {PWRu} complex. Attempts to substitute N for CHCN in the presence of an NaN excess lead a variety of products: (i) [PWO{Ru(N)}] (); (ii) [PWO{Ru(NHC-CH)}] () as a click-reaction product; and (iii) [PWO{Ru(N)}] ().

Heteroleptic Ruthenium(II) Complexes with Bathophenanthroline and Bathophenanthroline Disulfonate Disodium Salt as Fluorescent Dyes for In-Gel Protein Staining.

The in-gel detection of proteins for various proteomic experiments is commonly done with the fluorescent Ru tris(bathophenanthroline disulfonate) complex (Ru(BPS)), which is more cost-effective compared to commercial Ru-based formulations but requires tedious procedures for its preparation and strongly acidic staining conditions. Herein, we report the synthesis and characterization of heteroleptic Ru complexes Ru(BPS)(BP) and Ru(BPS)(BP) containing bathophenanthroline (BP) and bathophenanthroline disulfonate disodium salt (BPS) in comparison with Ru(BPS). It was shown by fluorescent and UV-vis measurements that novel Ru complexes were excitable in both UV and visible light, close to emission bands of classical lasers, which is important for successful in-gel protein detection.

WS /MoS Heterostructures through Thermal Treatment of MoS Layers Electrostatically Functionalized with W S Molecular Clusters.

The preparation of 2D stacked layers combining flakes of different nature gives rise to countless numbers of heterostructures where new band alignments, defined at the interfaces, control the electronic properties of the system. Among the large family of 2D/2D heterostructures, the one formed by the combination of the most common semiconducting transition metal dichalcogenides, WS /MoS , has awakened great interest owing to its photovoltaic and photoelectrochemical properties. Solution as well as dry physical methods have been developed to optimize the synthesis of these heterostructures.

Is It Possible To Prepare a Heterometal Anderson-Evans Type Anion?

Reaction of [SbWO] with [Pt(HO)(OH)] results in the first example of the mixed addenda Anderson-Evans type Pt{Sb(OH)}WO] anion, isolated and characterized as KNa[Pt{Sb(OH)}WO](NO)(OH)11HO ().

Reactions of [Ru(NO)Cl] with pseudotrilacunary {XWO} (X = As, Sb) anions.

Reactions of [Ru(NO)Cl] with pseudotrivacant B-α-[XWO] (X = As, Sb) at 160 °C result in the rearrangement of polyoxometalate backbones into {XM} structures. In the case of arsenic, oxidation of As to As takes place with the formation of a mixture of plenary and monosubstituted Dawson [AsWO] and [AsWRu(NO)O] anions, of which the latter was isolated as MeNH (DMA-1a and DMA-1b) and BuN (BuN-1) salts and fully characterized. Both α and α isomers of [AsWRu(NO)O] were present in the reaction mixture; pure [α-AsWRu(NO)O] was isolated as the BuN salt.

Interaction of Hydrophobic Tungsten Cluster Complexes with a Phospholipid Bilayer.

Nanoconstructions composed of lipid vesicles and inorganic units (nanoparticles, metal complexes) arouse much interest across materials science and nanotechnology as hybrid materials combining useful functionalities from both parts. Ideally, these units are to be embedded into the bilayer to keep the biophysical performance of lipid vesicles having inorganic moieties screened from the environment. This can be achieved by doping a lipid bilayer with cluster complexes of transition metals.

Investigation of electronic structure of tri- and tetranuclear molybdenum clusters by X-ray photoelectron and emission spectroscopies and quantum chemical methods.

Charge state studies of compounds [MoS(tu)(HO)]Cl·4HO (1), [MoSCl(dbbpy)]Cl·5HO (2), [MoS(CuCl)Cl(dbbpy)][CuCl] (3), containing {MoS} and {MoCuS} cluster cores bearing terminal thiourea (tu) or 4,4'-di-tert-butyl-2,2'-bipyridine (dbbpy) ligands, have been performed by X-ray photoelectron and X-ray emission spectroscopies combined with quantum chemical calculations. The best agreement between theory and experiments has been obtained using the B3LYP method. According to the experimental and calculated data, the Mo atoms are in the oxidation state 4+ for all compounds.

A new family of clusters containing a silver-centered tetracapped [Ag@Ag(μ-P)] tetrahedron, inscribed within a N icosahedron.

An unprecedented silver-centered P-tetracapped [Ag@Ag(μ-P)] tetrahedron inscribed within a N icosahedral cage has been discovered in the novel family of luminescent clusters. The latter are easily self-assembled by reacting Ag salts with tris(2-pyridyl)phosphine (PyP).

Kinetics Aspects of the Reversible Assembly of Copper in Heterometallic MoCuS Clusters with 4,4'-Di-tert-butyl-2,2'-bipyridine.

Treatment of the triangular [MoSCl(dbbpy)]Cl cluster ([1]Cl) with CuCl produces a novel tetrametallic cuboidal cluster [Mo(CuCl)SCl(dbbpy)][CuCl] ([2][CuCl]), whose crystal structure was determined by X-ray diffraction (dbbpy = 4,4'-di-tert-butyl-2,2'-bipyridine). This species, which contains two distinct types of Cu(I), is the first example of a diimine-functionalized heterometallic MM'S cluster. Kinetics studies on both the formation of the cubane from the parent trinuclear cluster and its dissociation after treatment with halides, supported by NMR, electrospray ionization mass spectrometry, cyclic voltammetry, and density functional theory calculations, are provided.

On the Critical Effect of the Metal (Mo vs. W) on the [3+2] Cycloaddition Reaction of M3 S4 Clusters with Alkynes: Insights from Experiment and Theory.

Whereas the cluster [Mo3 S4 (acac)3 (py)3 ](+) ([1](+) , acac=acetylacetonate, py=pyridine) reacts with a variety of alkynes, the cluster [W3 S4 (acac)3 (py)3 ](+) ([2](+) ) remains unaffected under the same conditions. The reactions of cluster [1](+) show polyphasic kinetics, and in all cases clusters bearing a bridging dithiolene moiety are formed in the first step through the concerted [3+2] cycloaddition between the C≡C atoms of the alkyne and a Mo(μ-S)2 moiety of the cluster. A computational study has been conducted to analyze the effect of the metal on these concerted [3+2] cycloaddition reactions.

Mechanism of [3+2] cycloaddition of alkynes to the [Mo3 S4 (acac)3 (py)3 ][PF6 ] cluster.

A study, involving kinetic measurements on the stopped-flow and conventional UV/Vis timescales, ESI-MS, NMR spectroscopy and DFT calculations, has been carried out to understand the mechanism of the reaction of [Mo3 S4 (acac)3 (py)3 ][PF6 ] ([1]PF6 ; acac=acetylacetonate, py=pyridine) with two RCCR alkynes (R=CH2 OH (btd), COOH (adc)) in CH3 CN. Both reactions show polyphasic kinetics, but experimental and computational data indicate that alkyne activation occurs in a single kinetic step through a concerted mechanism similar to that of organic [3+2] cycloaddition reactions, in this case through the interaction with one Mo(μ-S)2 moiety of [1](+) . The rate of this step is three orders of magnitude faster for adc than that for btd, and the products initially formed evolve in subsequent steps into compounds that result from substitution of py ligands or from reorganization to give species with different structures.

Photogeneration of hydrogen from water by hybrid molybdenum sulfide clusters immobilized on titania.

Two new hybrid molybdenum(IV) Mo3 S7 cluster complexes derivatized with diimino ligands have been prepared by replacement of the two bromine atoms of [Mo3 S7 Br6 ](2-) by a substituted bipyridine ligand to afford heteroleptic molybdenum(IV) Mo3 S7 Br4 (diimino) complexes. Adsorption of the Mo3 S7 cores from sample solutions on TiO2 was only achieved from the diimino functionalized clusters. The adsorbed Mo3 S7 units were reduced on the TiO2 surface to generate an electrocatalyst that reduces the overpotential for the H2 evolution reaction by approximately 0.