Thionation of the beta-oxo-delta-diimine (BODDI) 3 with P2S5 & centerdot;2Py affords the ditopic beta-thio-delta-diimine (BTDDI) 4. Based on H-1 NMR spectroscopy and single-crystal X-ray diffraction, 4 is best described as a bis(beta-enamine)-thione in both solution and the solid state. Furthermore, 4 features a thermochromic behavior in solution (c > 2 mmol l(-1)) and as a solid. Reaction with trimethyl aluminium readily affords the bimetallic dimethylaluminium BTDDI complex 5. In contrast to its oxygen relative, 5 is only weakly emissive and the emission is significantly red-shifted. Scalar-relativistic time-dependent density functional theory calculations suggest that introduction of the sulfur atom promotes an intersystem crossing pathway (similar to 1 ns) to low-lying and non-emissive triplet states, which competes with fluorescence (similar to 5 ns).

The synthesis of the monomeric alanediyl MSFluindtBuAl is reported. Its molecular structure is established by single-crystal X-ray diffraction and NMR spectroscopy, supported by theoretical calculations. MSFluindtBuAl features a singly-bonded aluminium(I) atom that is stabilized by an s-hydrindacene substituent.

The synthesis of 4,4′‐di‐ tert ‐butyl‐4 H ,4′ H ‐2,2′‐spirobi[benzo[ d ][1,3,2]dioxagermine] ( 1 ) and 4,4′,8,8′‐tetra‐ tert ‐butyl‐4 H ,4′ H ‐2,2′‐spirobi[benzo[ d ][1,3,2]dioxagermine] ( 2 ) being the first representatives of spirocyclic germanium salicyl alcoholates is reported. The reaction of these compounds with potassium fluoride in the presence of 18‐crown‐6 gives the alkoxido fluorido germanates [K(CH 2 CH 2 O‐) 6 ][GeF{OC 6 H 4 (CH t BuO)‐2} 2 ] ( 3 ) and [K(CH 2 CH 2 O–) 6 ][GeF{OC 6 H 3 (CH t BuO)‐2‐ t Bu‐6} 2 ] ( 4 ). All compounds are characterized including single crystal X‐ray diffraction analysis, nuclear magnetic resonance spectroscopy [ 1 H, 13 C{ 1 H}, 1 H– 13 C{ 1 H} heteronuclear single quantum coherence, and 19 F ( 3 and 4 )], infrared spectroscopy, and thermal analyzes. Single crystal X‐ray diffraction analyzes unveil a change of chirality in the salicyl alcoholate moieties of 3 with respect to the dominant (≈66%) stereoisomer of 1 upon crystallization as a result of fluoride‐induced ligand exchange equilibria. Reactivity studies of the compounds 1 and 2 are discussed in comparison with structurally related silicon‐based twin monomers.

Treatment of {Zr}( η 2 ‐Me 3 SiC≡CSiMe 3 )(py) ({Zr}=Zr( η 5 ‐C 5 H 5 ) 2 ; py=C 5 H 5 N) ( 1 ) with FcC(O)H (Fc=Fe( η 5 ‐C 5 H 5 )( η 5 ‐C 5 H 4 )) ( 2 a ) gives dimeric [{Zr}( η 2 ‐OCHFc)] 2 ( 3 ), while the reaction of 1 with ketone FcC(O)Ph ( 2 b ) produces monomeric metallaoxiran [{Zr}( η 2 ‐OCPhFc)(Ph)] ( 4 ). In contrast, compound 1 forms [{Zr}(O=CFc 2 ) 2 ] ( 5 ) in presence of FcC(O)Fc ( 2 c ). The structures of 3 – 5 in the solid state were determined by single crystal X‐ray analysis. In 3 two {Zr}( η 2 ‐OCHFc) building blocks are connected to each other over oxygen bridges with the aldehydes being η 2 ‐coordinated. By exchanging aldehyde 2 a by ketone 2 b , monomeric 4 is accessible with a σ ‐bonded phenylate ligand and a ketone bonded in a η 2 ‐fashion to Zr(IV). In contrast, within 5 two Fc 2 C=O ketones are datively bonded to a zirconocene unit with Zr in the oxidation state II, demonstrating a new family of compounds in which metallocene ketones are coordinated to a group 4 metal. Further, compounds 3 – 5 were characterized by IR spectroscopy and 3 , 4 were investigated by matrix assisted laser desorption/ionization mass spectrometry. In case of 5 , its crystallisation was tracked by NMR spectroscopy and its reaction towards CH 2 Cl 2 was investigated by high resolution mass spectrometry.

More than 100 years ago, B. N. Menshutkin systematically studied phase diagrams of antimony(III) halides with aromatic hydrocarbons for the first time, leading to the discovery of what is known today as Menshutkin complexes. As an extension to the wide variety of these Pnpi arene type complexes, which have been nicely reviewed by Schmidbaur and Schier in 2008, a series of isomorphous compounds with diphenylethane derivatives as organic linkers in supramolecular networks are reported. By setting up a library of complexes consisting of PnX3 (Pn = Sb, Bi; X = Cl, Br) and (2-R-C6H4)C2H4(2-R-C6H4) (R = Me, Br, NH2, NO2), the structures of five new Menshutkin complexes and six additionally isolated SbR donor-acceptor type complexes are compared. Lewis basic R-groups favor the formation of donor-acceptor complexes whereas weaker ones lead to Pnpi arene complexes. The influence of the pnictogen atom (Pn), the halide (X), and the substituent (R) concerning Pnpi arene distances in the solid state of the isomorphous Menshutkin complexes is examined. The results are discussed in view of previous studies providing a deeper insight into the qualitative and quantitative nature of Pnpi arene interactions.

A new pyrazol-chromeno[2,3-d]pyrimidine compound, 7-bromo-5-(5-hydroxy-3-methyl-1H-pyrazol-4-yl)-1,5-dihydro-2H-chromeno[2,3-d]pyrimidine-2,4(3H)-dione (Br-PCP) was obtained in the three-component reaction of pyrazolone, 5-bromosalicylaldehyde, and barbituric acid. The reaction was performed in the presence of tartaric acid, using a refluxed mixture of water: ethanol (4:1v/v) for 3 h Br-PCP was obtained in very good yield (75 %), and characterized by elemental analysis, IR, NMR, and UV-Vis spectroscopy, as well as by a single crystal X-ray diffraction study. Additionally, theoretical calculations were used to support and to reinforce experimentally obtained analytical data (IR, H-1 NMR, C-13 NMR, and UV-Vis). The interaction of Br-PCP with bovine serum albumin (BSA) has been investigated using temperature-dependent fluorescence and molecular docking study. The obtained binding constant indicates the moderate type of association of ligand to protein, and thermodynamic parameters show that the binding process is spontaneous and occurs via van der Waals and hydrogen bonding interactions. Molecular docking results explain the connecting of BSA to the ligand and it is consistent with the experimentally obtained results. Also in this study, the dipole moment, polarizability, and first order hyperpolarizability were calculated in order to determine the nonlinear optical (NLO) activity of the title molecule. First order hyperpolarizability results validated the molecule's nonlinear optical activity.

Bifunctional N-heterocyclic carbenes (NHCs) with additional hydrogen bond donor groups in the backbone are important organocatalysts and ligands for transition metal complexes. Herein, a straightforward synthetic approach to a library of bifunctional imidazolium salts, precursors for the respective NHCs with amidine, squaramide, and (thio)urea moieties as hydrogen bond donors, is reported. The preparation of bifunctional palladium(II) and copper(I) NHC complexes and their application in catalysis is presented.

The synthesis, structure and thermal decomposition behaviour of unique mononuclear, homoleptic [pipH] 3 [Cu (O 2 CH) 5 ] ( 2 ) (pipH + = piperidinium) is discussed in which the copper(II) ion is exclusively coordinated by five formate anions forming a distorted square-pyramidal coordination sphere. Thermogravimetric studies confirmed a comparatively low decomposition temperature ( T onset = 107 degrees C) affording solely elemental Cu. Based on TG -MS experiments a decomposition mechanism is presented.

The (pentamethylcyclopentadienyl)chloridoiridium(III) complex bearing a κP,κS-bonded Ph2PCH2CH2SPh ligand ([Ir(η5-C5Me5)Cl(Ph2P(CH2)2SPh-κP,κS)]PF6, (1)] was synthesized and characterized. Multinuclear (1H, 13C and 31P) NMR spectroscopy was employed for the determination of the structure. Moreover, SC-XRD confirmed the proposed structure belongs to the “piano stool” type. The Hirshfeld surface analysis outlined the most important intermolecular interactions in the structure. The crystallographic structure was optimized at the B3LYP-D3BJ/6-311++G(d,p)(H,C,P,S,Cl)/LanL2DZ(Ir) level of theory. The applicability of this level was verified through a comparison of experimental and theoretical bond lengths and angles, and 1H and 13C NMR chemical shifts. The Natural Bond Orbital theory was used to identify and quantify the intramolecular stabilization interactions, especially those between donor atoms and Ir(III) ions. Complex 1 was tested on antitumor activity against five human tumor cell lines: MCF-7 breast adenocarcinoma, SW480 colon adenocarcinoma, 518A2 melanoma, 8505C human thyroid carcinoma and A253 submandibular carcinoma. Complex 1 showed superior antitumor activity against cisplatin-resistant MCF-7, SW480 and 8505C cell lines. The mechanism of tumoricidal action on 8505C cells indicates the involvement of caspase-induced apoptosis, accompanied by a considerable reduction in ROS/RNS and proliferation potential of treated cells.

Abstract Mono-coordinated metallyenes (R–M:) of the Group 13 elements feature a non-bonding pair of electrons together with two vacant orbitals, which makes them highly reactive ambiphiles that readily activate small molecules by oxidative addition. In consequence of their pronounced reactivity, examples of mono-coordinated organometallics of aluminium(I) and gallium(I) remain rare. Here, we report the one-step synthesis of a monomeric gallium(I) compound that readily undergoes oxidative addition reactions and, more remarkably, carbometalation reactions with alkynes by retention of the low oxidation state +I and the coordination number one at gallium. This contrasts previous reports on the reactivity of low-valent main-group compounds, which are regularly oxidized to compounds in a more stable higher oxidation state. These findings provide a new approach to access low-valent main-group compounds and pave the way for the development of novel bond-functionalisation strategies that hence could enable the development of new catalytic processes in the future.

Ferrocenyl–triazoles synthesized, characterized and electrochemically investigated. They uses as modifier for the screen printed carbon electrodes proven toward cations sensing.

Using the pentadentate tetrapyrazolylpyridyl diborate (B2Pz4Py) ligand allowed for the isolation of overall seven group 13 complexes, which have been fully characterised and whose solid-state structures were obtained by single-crystal X-ray diffraction analysis. The aluminium chloride (1) and bromide (2) complexes as well as the gallium chloride (3) and iodide (4) complexes are accessible by deprotonation of the ligand precursors [B2Pz4LiPyH]2 with lithium hexamethyldisilazide and subsequent reaction with aluminium and gallium trihalides. Using indium(I) chloride instead gives rise to the indium(III) bis(trimethylsily)amide complex 5. Chloride abstraction from the aluminium(III) complex 1 using a combination of TlBArF24 and TlPF6 affords the related aluminium(III) fluoride complex 6 while using the gallium(III) complex 3 yields the dinuclear cationic PF2O2-bridged gallium(III) complex 7.

The tetrapyrazolylpyridyl diborate (B(2)Pz(4)Py) ligand provides a suitable platform for the isolation of heterobimetallic main-group element compounds as well as homotetrametallic copper complexes. The heterobimetallic tin(II)-lithium(I) (1) and tin(II)-thallium(I) (2) complexes have been synthesized, isolated, and fully characterized including single-crystal X-ray diffraction analysis. When reacted with copper(I) sources, complex 2 grants access to a homotetrametallic copper(I) complex (4). Upon subsequent oxidation, 4 gives rise to the bimetallic copper(II) complex 5, in which the two copper(II) centers are connected via a bridging bromido ligand (Cu-II-mu-Br-Cu-II).

AbstractEnhancing the supercapacitors’ performance relies on the increased capacitance and voltage window, which are the current key challenges for developing new materials. In this study, the mononuclear NiII‐bis(oxamato) complex ([nBu4N]2[Ni(opba)], 1) has been synthesized and used as a template in polypyrrole (PPy) based conductive polymer as a novel electrode material for supercapacitor applications. The surface and structural properties of PPy and PPy/1 electrodes were studied using SEM and TEM to elucidate their interactions. The results of characterization techniques revealed that complex 1 altered the morphology, creating a prominent three‐dimensional globular structure in the PPy/1 hybrid material without significant chemical modification. The electrochemical properties of PPy and PPy/1 were investigated by CV, EIS, and GCD analyses. The PPy/1 electrode demonstrated intense pseudocapacitive behavior, showing a significantly widened potential window and increased current compared to the PPy electrode, resulting in enhanced energy storage capacity within the material. This improvement was evaluated by testing a symmetric supercapacitor in a coin cell architecture with an alginate‐based gel acting as both electrolyte and separator. The maximum specific cell capacitance reached 41.6 F g−1 at a current density of 0.2 A g−1, with a remarkable capacity retention of 97 % after 1000 galvanostatic charge/discharge cycles.

Unsymmetrically N,N'-substituted metal amides of silicon, germanium and aluminium were synthesized starting from N-ethyl-2-(n-propylaminomethyl)phenylamine (1, Et,nPr-ampaH2). Reaction of the dilithium compound of 1 with SiCl4 gave spirocyclic Si(Et,nPr-ampa)2 (2) and Cl2Si(Et,nPr-ampa) (3). Reduction of 3 with potassium resulted in the formation of the corresponding cyclotetrasilane [Si(Et,nPr-ampa)]4 (4), whereas the reaction of 3 with lithium triethylborohydride gave the dihydro silane H2Si(Et,nPr-ampa) (5). The corresponding germanium(IV) compounds Ge(Et,nPr-ampa)2 (6) and Cl2Ge(Et,nPr-ampa) (7) were synthesized starting from GeCl4, amine 1 and NEt3 using appropriate stoichiometric ratios. Reaction of Ge[N(SiMe3)2]2 with amine 1 provided the germylene [Ge(Et,nPr-ampa)]2 (8). The aluminium dichloro compound Cl2Al(Et,nPr-ampaH) (9) was obtained either by reaction of the dichlorogermine 7 with lithium aluminium hydride or by reaction of the dilithium salt of 1 with AlCl3. Reaction of trimethylaluminium with amine 1 provided the amido-amine (CH3)2Al(Et,nPr-ampaH) (10) which was converted into the diamide CH3Al(Et,nPr-ampa) (11) by methane elimination.

The synthesis and characterization of twin monomers [Ti(OCH2-2-MeO-C6H4)(4)(HOCH2-2-MeO-C6H4)](2) (3) and [Al(OCH2-2-MeO-C6H4)(3)](4) (5) by reacting HOCH2-2-MeO-C6H4 (1) with Ti((OPr)-Pr-i)(4) (2), or 1 with AlMe3 (4) is discussed. Single crystal X-ray structure analysis of 3 shows a dimeric structure with two alkoxide ligands bridging the titanium ions, while the others are terminal bonded. The respective phenolic resin / metal oxide hybrid materials HM_Ti and HM_Al were obtained in moderate (HM_Ti) to excellent (HM_Al) yields using typical base-catalyzed twin polymerization conditions (230 degrees C, 2 h). Nuclear magnetic resonance and infrared spectroscopy as well as scanning electron microscopy and scanning transmission electron microscopy combined with energ-dispersive X-ray spectroscopy proved the formation of inorganic-organic hybrid materials consisting of resin and MxOy materials (HM_Ti, TiO2; HM_Al, Al2O3) containing interpenetrating phase nano-domains with sizes of < 5 nm, as is charcteristic for twin polymerization processes. Oxidation of HM_Ti and HM_Al yielded the respective oxide materials Ox_Ti (TiO2) and Ox_Al (Al2O3), which possess low surface areas of A(BET) = 53 m(2)/g and 76 m(2)/g, respectively.

Objectives: New tributyltin(IV) complexes containing the carboxylate ligands 3-(4-methyl-2-oxoquinolin-1(2H)-yl)propanoic acid (HL1) and 2-(4-methyl-2-oxoquinolin-1(2H)-yl)acetic acid (HL2) have been synthesized. Methods: Their structures have been determined by elemental microanalysis, FT-IR and multinuclear NMR (1H, 13C and 119Sn) spectroscopy and X-ray diffraction study. A solution state NMR analysis reveals a four-coordinated tributyltin(IV) complex in non-polar solvents, while an X-Ray crystallographic analysis confirms a five-coordinated trigonal-bipyramidal geometry around the tin atom due to the formation of 1D chains. A theoretical structural analysis was performed by optimization employing B3LYP-D3BJ functional and 6-311++G(d,p)/def2-TZVP(Sn) basis sets for H, C, N, O/Sn, respectively. The interactions between tin(IV) and surrounding atoms were examined by QTAIM approach. The in vitro antiproliferative activity of the synthesized compounds was evaluated by MTT and CV assays versus MCF-7 (human breast adenocarcinoma), HCT116 (human colorectal carcinoma), A375 (human melanoma), 4T1 (mouse breast carcinoma), CT26 (mouse colon carcinoma) and B16 (mouse melanoma) tumor cell lines. Results: Both synthesized compounds (nBu3SnL1 and nBu3SnL2) exerted powerful micromolar IC50 cytotoxicity values and demonstrated high selectivity toward malignant cells. Both experimental drugs affected cell adhesion and induced anchorage independent apoptosis, a favorable type of cell death with an essential role in cancer dissemination prevention. The BSA-binding affinity of the obtained organotin compounds was followed by spectrofluorometric titration and molecular docking simulations. Conclusions: The tributyltin(IV) compounds selectively induce anoikis-like cell death in A375 cells, also highlighting the importance of the organic moiety on the tin(IV) ion in the mechanism of action.

A novel trimethyltin(IV) complex (Me3SnL), derived from 3-(4-methyl-2-oxoquinolin-1(2H)-yl)propanoate ligand, has been synthesized and characterized by elemental microanalysis, UV/Vis spectrophotometry, FT-IR and multinuclear (1H, 13C and 119Sn) NMR spectroscopies. Furthermore, the structure of the ligand precursor HL was solved using SC-XRD (single-crystal X-ray diffraction). The prediction of UV/Vis and NMR spectra by quantum-chemical methods was performed and compared to experimental findings. The protein binding affinity of Me3SnL towards BSA was determined by spectrofluorometric titration and subsequent molecular docking simulations. Me3SnL has been evaluated for its in vitro anticancer activity against three human cell lines, MCF-7 (breast adenocarcinoma), A375 (melanoma) and HCT116 (colorectal carcinoma), and three mouse tumor cell lines, 4T1 (breast carcinoma), B16 (melanoma) and CT26 (colon carcinoma), using MTT and CV assays. The strong inhibition of A375 cell proliferation, ROS/RNS upregulation and robust lipid peroxidation lead to autophagic cell death upon treatment with Me3SnL.

Bulk quantities of “helmet” type phthalogens are now achievable with broad variation of their substituents allowing to study their thermal and electrochemical decomposition to CoPcs.

The reaction of the ferrocene derivative Fe(eta 5-C5H4CO2H)(eta 5-C5H4CH=CH2) (=fcCO2H) (1) with the zinc reagents [Zn(OAc)2]center dot xH2O (OAc = acetate; 2a, x = 0; 2b, x = 2) or ZnEt2 (3) in non-aqueous solvents toluene or tetrahydrofuran resulted in the formation of the cluster [Zn4O(fcCO2)6] (4). The structure of 4 in the solid state has been determined by single-crystal X-ray diffraction analysis. Cluster 4 crystallizes in the triclinic space group P 1. In 4, the cluster core is set-up by four zinc(II) ions which are forming the vertices of a tetrahedron with a mu 4-oxygen atom in its center. Six mu-fcCO2 units bridge the edges of the tetrahedron. IR spectroscopy confirms with triangle nu CO2 = 91 cm-1 (triangle nu CO2 = nu CO2,asym - nu CO2,sym) the mu-bridging character of the fcCO2 entities. Cyclic voltammetry studies showed a reversible redox event at E degrees ' = 245 mV versus FcH/FcH+ (FcH = Fe(eta 5-C5H5)2) for 4 with the six fcCO2 redox events superimposed. High-resolution ESI-TOF measurements verified the identity of 4.