Structure and properties evolution with inorganic and organic acids of a new organo-chlorocadmate compound (C6H20N3)2[Cd2Cl10] : theoretical approach

This work was supported by the Ministry of Higher Education and Scientific Research of Tunisia.This work describes the theoretical studies of the reactivity, electrical and thermodynamic properties of a novel organo-chlorocadmate complex (C6H20N3)2[Cd2Cl10] and its inorganic and organic acid derivatives. The synthesis and crystal structure are described, with the compound crystallizing in the orthorhombic (Pnma) space group with unit cell parameters: a = 7.25494(11) Å, b = 29.3000(5) Å, c = 7.33927(13) Å. The semi-empirical calculations reveal that not only are all of the derivatives semiconductors, but also that the inclusion of acids in the structure alter the electrical and thermodynamic properties significantly, demonstrating a systematic and easy method for tuning the materials reactivity along with other desirable properties.PostprintPeer reviewe

Constrained phosphine chalcogenide selenoethers supported by peri-substitution

A series of phosphorus and selenium peri-substituted acenaphthene species with the phosphino group oxidized by O, S, and Se has been isolated and fully characterized, including by single-crystal X-ray diffraction. The P(V) and Se(II) systems showed fluxional behavior in solution due to the presence of two major rotamers, as evidenced with solution NMR spectroscopy. Using Variable-Temperature NMR (VT NMR) and supported by DFT (Density Functional Theory) calculations and solid-state NMR, the major rotamers in the solid and in solution were identified. All compounds showed a loss of the through-space JPSe coupling observed in the unoxidized P(III) and Se(II) systems due to the sequestration of the lone pair of the phosphine, which has been previously identified as the major contributor to the coupling pathway.Publisher PDFPeer reviewe

(Decacarbonyl)(1-isopropyl-2-phenyl-1,2,5,6-tetrahydroacenaphtho [5,6-cd][1,2]diphosphole)ditungsten(0) : Molbank

A binuclear tungsten(0) complex with an asymmetric bridging 1,2-diphosphole ligand was prepared by the photolysis of tungsten hexacarbonyl in the presence of 1-isopropyl-2-phenyl-1,2,5,6-tetrahydroacenaphtho [5,6-cd][1,2]diphosphole. The tungsten complex 1 was characterized by high resolution mass spectrometry, multinuclear NMR spectroscopy (1H, 13C, 31P), and elemental microanalysis. The structure of the trans isomer was resolved by single crystal X-ray diffraction, showing a slight elongation of the P−P bond upon coordination to the W(CO)5 groups.Publisher PDFPeer reviewe

Morphology- and size-controlled synthesis of a metal-organic framework under ultrasound irradiation : an efficient carrier for pH responsive release of anti-cancer drugs and their applicability for adsorption of amoxicillin from aqueous solution

Support of this investigation by Tarbiat Modares University is gratefully acknowledged.In this study, we have reported a biocompatible metal-organic framework (MOF) with ultra-high surface area, which we have shown to have uses as both a cancer treatment delivery system and for environmental applications. Using a sonochemical approach, highly flexible organic H3BTCTB and ditopic 4,4́′-BPDC ligands, along with modulators of acetic acid and pyridine were combined to prepare a Zn(II)-based metal-organic framework, DUT-32, [Zn4O(BPDC)(BTCTB)4/3(DEF)39.7(H2O)11.3]. Powder X-ray diffraction (PXRD), field-emission scanning electron microscopy (FE-SEM), and Fourier transform infrared spectroscopy (FTIR) were used to characterize, the particle size, shape, and structure of the DUT-32. To show the effects of shape and size of DUT-32 micro/nano-structures on doxorubicin (DOX) drug release and amoxicillin (AMX) adsorption, time of sonication, initial reagent concentrations, irradiation frequency, and acetic acid to pyridine molar ratios were optimized. The drug-loaded DUT-32 was soaked in simulated body fluid (SBF) and the drug release ratio was monitored through release time to perform in vitro drug release test. A slow and sustained release was observed for DUT-32 micro/nano-structures, having a considerable drug loading capacity. At the pH values 7.4-4.5, various profiles of pH-responsive release were achieved. Also, the prepared DUT-32 micro/nano-structures are found to be biocompatible with PC3 (prostate cancer) and HeLa (cervical cancer) cell lines, when tested by MTT assay. Moreover, DUT-32 micro/nano-structures were studied to show AMX adsorption from aqueous solution. Finally, kinetic studies indicated that AMX adsorption and drug release of DOX via this MOF are of first-order kinetics.PostprintPeer reviewe

1,4-Diiodotetrafluorobenzene 3,5-di-(pyridin-4-yl)-1,2,4-thiadiazole <1/1>

The reactivity of 3,5-di-(pyridin-4-yl)-1,2,4-thiadiazole (L1) with 1,4-diiodotetrafluorobenzene (1,4-DITFB) was explored and the halogen-bonded 1:1 co-crystal (1) was successfully isolated and structurally characterized

Thionylimido complexes

An improved route to d-block and main group NSO complexes is presented including the synthesis of the first antimony(V) complexes, (Ar3Sb(NSO)2), and copper examples (CuBipy(PPh3)NSO). The structures of eight complexes are reported. The observed variation in M-N-S bond angles is due to the combination of orbital overlap (ligand-to-metal bonding) and the degree of ionicity of the bonding.Publisher PDFPeer reviewe

A cascade Suzuki-Miyaura/Diels-Alder protocol : exploring the bifunctional utility of vinyl Bpin

Funding: Industrial CASE studentship awarded from EPSRC and GlaxoSmithKline. The authors thank the EPSRC, GlaxoSmithKline, and the University of St Andrews for studentship funding (DLC), and the University of St Andrews and the EPSRC UK National Mass Spectrometry Facility at Swansea University for analyses.Cascade reactions are an important strategy in reaction design, allowing streamlining of chemical synthesis. Here we report a cascade Suzuki-Miyaura/Diels-Alder reaction, employing vinyl Bpin as a bifunctional reagent in two distinct roles: as an organoboron nucleophile for cross- coupling and as a Diels-Alder dienophile. Merging these two reactions enables a rapid and operationally simple synthesis of functionalized carbocycles in good yield. The effect of the organoboron subtype on Diels- Alder regioselectivity was investigated and post-synthetic modifications were carried out on a model substrate. The potential for a complementary Heck/Diels-Alder process was also assessed.PostprintPeer reviewe

Synthesis, spectroscopic, and structural characterization of new functionalized gem-bisphosphonate complexes of tin(IV) chloride

The authors are grateful to the Tunisian Ministry of High Education and Scientific Research and Technology for financial support of this researchBisphosphonates of the types X(P(O)(OEt)2)2 (X = CH2=C (1a), CNCH2CH (1b) and PhCH2NCH2CH (1c)) react with SnCl4 in anhydrous dichloromethane to produce the new tin(IV) adducts [SnCl4(1a)] (2a), [SnCl4(1b)] (2b) and [SnCl4(1c)] (2c) in 72-80% yields. These complexes were characterized using IR, multinuclear (1H, 13C, 31P, 119Sn) NMR spectroscopy, elemental analysis, and in one case by single crystal X-ray diffraction. The NMR data show that the bisphosphonate ligands are coordinated to the tin center in a bidentate fashion forming cis octahedral tin complexes. Furthermore, the X-ray structure of complex 2b reveals that the bisphosphonate ligand is coordinated in a bidentate manner to the metal center in a distorted octahedral arrangement with Sn-O-P bond angles in the range 135.95(16)–137.99(18)°. The P=O and Sn-O bond lengths of 1.495(3)-1.497(3) and 2.134(3)-2.146(2) Å, respectively are in the order expected for phosphonate tin(IV) complexes. The results are discussed and compared with closely related analogues.PostprintPeer reviewe

Simple and inexpensive method for the detection of carbon monoxide released from thermal cheletropic decarbonylation reactions

This work presents a simple protocol that demonstrates the use of an inexpensive household carbon monoxide detector as a useful tool to detect the release of carbon monoxide gas from thermal cheletropic decarbonylation reactions. The carbon monoxide detection method described has been employed in a short series of reactions used in a university teaching laboratory setting, and full procedures for these are outlined. In each case, the procedure to isolate and identify the decarbonylation products has also been provided.PostprintPeer reviewe

A simplified extractive metallurgy exercise to demonstrate selective extraction of copper

A laboratory activity is described for senior high school or 1st year undergraduate level students that illustrates key concepts linked to extractive metallurgy. This experiment demonstrates preferential binding of a methoxyphenolic oxime ligand to Cu2+ in the presence of other transition metal ions in aqueous solution. The students are tasked to investigate the importance of the spatial relationship between the oxime and phenol group of two potential ligands by performing a series of short and simple tests. The objective is achieved by identifying which methoxyphenolic oxime ligand selectively and rapidly forms an isolable precipitate with Cu2+ ions. Only one of the potential ligands exhibits a clear preference for binding to Cu2+ and this can easily be identified visually (and confirmed by UV-visible spectroscopy if desired). The experiment has successfully been employed as part of an extracurricular laboratory course involving groups of 25-30 high school students.PostprintPeer reviewe