Assembling Di- and Polynuclear Cu(I) Complexes with Rigid Thioxanthone-Based Ligands: Structures, Reactivity, and Photoluminescence.

Thioxanthone (TX) molecules and their derivatives are well-known photoactive compounds. Yet, there exist only a handful of luminescent systems combining TX with transition metals. Recently, we reported a TX-based PSP pincer ligand () that appears as a promising platform for filling this niche.

Cationic ligands - from monodentate to pincer systems.

For a long time, the small group of cationic ligands stood out as obscure systems within the general landscape of coordinative chemistry. However, this situation has started to change rapidly during the last decade, with more and more examples of metal-coordinated cationic species being reported. The growing interest in these systems is not only of purely academic nature, but also driven by accumulating evidence of their high catalytic utility.

Sulfonium Cation in the Service of π-Acid Catalysis.

While still rare, cationic ligands offer much promise as tunable electron-withdrawing ligands for π-acid catalysis. Recently, we introduced pincer-type sulfonium cations into the list of available strongly π-acidic ancillary ligands. However, the M-S bond in sulfonium complexes of these ligands was found highly labile, precluding their catalytic applications.

Effect of Internal Ligand Strain on Coordination Behavior of PSP Pincer Ligands.

Chelating ligands and most specifically pincer ligands, with their characteristic co-planar binding, usually undergo deformations upon coordination, resulting in a significant ligand strain. Such an effect on the properties of the so formed complex has rarely been explored. This study is an attempt to analyze this strain and its contribution to the overall binding energy and coordination behavior of PSP pincer ligands.

Sulfonium cations as versatile strongly π-acidic ligands.

More than a century old, sulfonium cations are still intriguing species in the landscape of organic chemistry. On one hand they have found broad applications in organic synthesis and materials science, but on the other hand, while isoelectronic to the ubiquitous tertiary phosphine ligands, their own coordination chemistry has been neglected for the last three decades. Here we report the synthesis and full characterization of the first Rh(i) and Pt(ii) complexes of sulfonium.

Synthesis, structural characterization, and bonding analysis of two-coordinate copper(I) and silver(I) complexes of pyrrole-based bis(phosphinimine): new metal-pyrrole ring π-interactions.

The reaction between 2,5-bis(diphenylphosphinomethyl)pyrrole and Me3SiN3 gave the new pyrrole-based bis(phosphinimine) L1H in an excellent yield. L1H reacts with [CuCl(COD)]2, AgBF4, or AgOTf to give the corresponding two-coordinate mononuclear ionic complex formulated as [M{(L1H)-κ2N,N}]+[X]- where M = Cu and Ag; X = [CuCl2], BF4 or OTf. Their single crystal X-ray diffraction studies confirmed the two-coordinate geometry formed by the chelate bonding mode of L1H.

Versatility of the bis(iminopyrrolylmethyl)amine ligand: tautomerism, protonation, helical chirality, and the secondary coordination sphere with halogen bonds in the formation of copper(II) and nickel(II) complexes.

The reaction of N,N-di(2,6-bis(isopropyl)phenylimino-pyrrolyl-α-methyl)-N-methylamine H2L1 with copper(i) sources such as CuX (X = Cl (1), Br (2), and I (3)) afforded bis(chelated) ionic copper(ii) complexes of the type [CuL1H]X. A similar type of mononuclear structure was obtained with Cu(NO3)2·(H2O)3. Conversely, binuclear copper(ii) complexes [Cu2(μ-L1)(μ-OOCCH3)(μ-OH)](4) and [Cu2(μ-L1H)(μ-OOCPh)(μ-O)] (5) were obtained from the reaction of Cu(O2CR)2·H2O with H2L1.

Crystal structure and DFT analyses of a pentacoordinated PCP pincer nickel(II) complex.

The reaction of NiCl with 1,3-bis[(diphenylphosphanyl)methyl]hexahydropyrimidine in the presence of 2,6-dimethylphenyl isocyanide and KPF afforded a new pentacoordinated PCP pincer Ni complex, namely {1,3-bis[(diphenylphosphanyl)methyl]hexahydropyrimidin-2-yl-κN}(2,6-dimethylphenyl isocyanide-κC)nickel(II) hexafluoridophosphate 0.70-hydrate, [Ni(CHN)(CHClNP)]PF·0.7HO or [NiCl{C(NCHPPh)(CH)-κP,C,P'}(Xylyl-NC)]PF·0.

Nickel(II) and Palladium(II) Complexes Bearing an Unsymmetrical Pyrrole-Based PNN Pincer and Their Norbornene Polymerization Behaviors versus the Symmetrical NNN and PNP Pincers.

Unsymmetrical pincers have been shown to be better than the corresponding symmetrical pincers in several catalysis reactions. A new unsymmetrical PNN propincer, 2-(3,5-dimethylpyrazolylmethyl)-5-(diphenylphosphinomethyl)pyrrole (1), was synthesized from pyrrole through Mannich bases in a good yield. In addition, the new byproduct 2-(3,5-dimethylpyrazolylmethyl)-5-(dimethylaminomethyl)- N-(hydroxymethyl)pyrrole was also isolated.

Facile synthesis of Pd(ii) and Ni(ii) pincer carbene complexes by the double C-H bond activation of a new hexahydropyrimidine-based bis(phosphine): catalysis of C-N couplings.

Hexahydropyrimidine-based bis(phosphine), a pro-NHC ligand, was synthesized in one step and excellent yield. It underwent spontaneous double C-H bond activation to give cationic pincer NHC complexes of the type [(PCP)MCl]X (M = Pd, Ni and X = Cl, BF4) in the absence of any external reagents. Their structures were determined by X-ray diffraction methods and the mechanism of formation of palladium carbene complexes as analyzed by DFT calculations showed two transition states.

Ultrasonic-assisted synthesis of graphene oxide - fungal hyphae: An efficient and reclaimable adsorbent for chromium(VI) removal from aqueous solution.

In this study, a hybrid film bio-nanocomposite material was developed based on the graphene oxide/fungal hyphae (GO-FH) interaction. The developed GO-FH bio-nanocomposite material was used for the removal of hexavalent chromium from aqueous solution. The GO-FH bio-nanocomposite material was prepared by ultrasonic irradiation technique.

Preparation of graphene oxide/chitosan/ferrite nanocomposite for Chromium(VI) removal from aqueous solution.

A magnetically modified graphene oxide/chitosan/ferrite (GCF) nanocomposite material was synthesized and exploited for removal of Chromium(VI) from aqueous solution. The GCF nanocomposite material was characterized by powder-X-ray diffraction (powder-XRD), Fourier transform infrared spectroscopy (FT-IR), scanning electron microscope- energy dispersive X-ray (SEM-EDX) analysis, transmission electron microscopy (TEM) thermogravimetric analysis (TGA), UV-vis diffusive reflectance spectra and Brunauer-Emmett-Teller (BET) analysis. The effect of pH, adsorbent dose, contact time and initial Cr(VI) metal ion concentration were studied in batch process.