Synthesis, Crystal Structures and Photoluminescent Properties of One-Dimensional Europium(III)- and Terbium(III)-Glutarate Coordination Polymers, and Their Applications for the Sensing of Fe3+ and Nitroaromatics

Acknowledgements X.C. thanks the National Natural Science Foundation of China (Grants No. 1771057 and U1804253). S.H. is grateful to Henan Normal University for a postdoctoral fellowship. Supplementary data CCDC numbers 1919755 and 1919756 for 1 and 2 respectively, contain the crystal data of this article. These data are available from Cambridge Crystallographic Data Centre via www.ccdc.cam.ac.uk/datarequest/cif. The supporting material of this article can be download from the journal webpage.Peer reviewedPublisher PD

Reactions of PNCNP and POCOP Pincer Platinum Hydride Complexes with Phenylacetylene and Carbon Disulfide: The Influence of the Pincer Backbone on the Structures of Unsaturated Auxiliary Ligands

In order to get information about the influence of the pincer backbone on the structure and reactivity of a pincer complex, bisphosphiamine PNCNP and bisphosphinite POCOP pincer platinum hydride complexes, [2,6-(tBu2PY)2C6H3]PtH (Y = NH, 1a; O, 2a), were reacted with phenylacetylene and carbon disulfide. The reactions with phenylacetylene in the presence of CuI/Et2NH produced the corresponding σ-alkynyl complexes [2,6-(tBu2PY)2C6H3]PtCCPh (Y = NH, 1b; O, 2b). The reactions with carbon disulfide produced the corresponding dithioformato complexes [2,6-(tBu2PY)2C6H3]PtSC(S)H (Y = NH, 1c; O, 2c). The PNCNP complex 1a is easier to react with carbon disulfide than the POCOP complex 2a. X-ray crystal structure analysis indicated that the PNCNP pincer backbone influences the phenylacetylido and dithioformato auxiliary ligands in the resulting complexes more significantly than the POCOP pincer backbone. The dithioformato auxiliary ligand adopts different coordination modes in complexes 1c and 2c. The results provide useful information about how PNCNP and POCOP pincer backbones influence the reactivity of the metal center and the coordination of unsaturated auxiliary ligands

An Effective Osmium Precatalyst for Practical Synthesis of Diarylketones: Preparation, Reactivity, and Catalytic Application of [OsH-<i>cis</i>-(CO)₂-<i>mer</i>-{κ³‑<i>P</i>,<i>B</i>,<i>P</i>′‑B(NCH₂PPh₂)₂‑<i>o</i>‑C₆H₄}]

Developing new approaches for efficient synthesis of diarylketones from commercially available inexpensive substrates via practical procedures is highly desirable. In this work, an effective catalytic system for the synthesis of diarylketones was developed based on a newly synthesized Os PBP pincer complex [OsH-cis-(CO)2-mer-{κ3-P,B,P′-B­(NCH2PPh2)2-o-C6H4}] (1). Complex 1 proved to be very stable against many reagents at room temperature; CS2 can only react with 1 at elevated temperatures to produce [Os­(κ2-S,S’-S2CH)­(CO)-mer-{κ3-P,B,P′-B­(NCH2PPh2)2-o-C6H4}] (2). Complex 1 was found to be an efficient precatalyst for the coupling reactions between arylboronic acids and aryl aldehydes. The reactions are tolerant of many functional groups and proceed smoothly in toluene in the presence of K3PO4 and H2O at 100 °C under an air atmosphere to give diaryl ketones in good to excellent yields. It was demonstrated that the reactions were catalyzed by in situ generated osmium nanoparticles. This work would open an avenue of heterogeneous transition metal catalyst system for the synthesis of diarylketones via the coupling reactions between arylboronic acids and aryl aldehydes, which has never been reported before

Catalytic effect of water on the HO₃ + NO formations from the HNO + O₃ reaction in tropospheric conditions

A comprehensive investigation of the roles of water catalysts on O3 with HNO in the troposphere has been carried out by quantum chemical calculations at the CCSD(T)/aug-cc-pVTZ//M06-2X/6-311++G(2d,2p) levels of theory. Besides, the AIMD (ab initio Molecular Dynamics) simulation also used to help us to understand the mechanism of this reaction. The results show that the HNO + O3 reaction undergoes a channel for the formation of NO + HO3 and overcomes the energy barrier of 1.60 kcal·mol−1. After adding water molecules, the obtained product did not change, but the potential energy surface was much more complicated than the bare reaction, and it went through four reaction channels of HNO···H2O + O3, H2O···HNO + O3, H2O···O3 + HNO and O3···H2O + HNO. Among them, the channel HNO···H2O + O3 is the dominant channel for water molecules to participate in the reaction. Overall, these results show how water catalyzed the gas-phase reactions under atmospheric conditions.</p

Practical Synthesis of B(9)-Halogenated Carboranes with <i>N</i>‑Haloamides in Hexafluoroisopropanol

The B­(9)-H halogenation of o-carborane and m-carborane was achieved with excellent selectivities in hexafluoroisopropanol (HFIP) under simple reaction conditions: single reagent [trichloroisocyanuric acid (TCCA), tribromoisocyanuric acid (TBCA) or N-iodosuccinimide (NIS)], catalyst-free, air-/moisture-tolerant, and convenient work-up. With this method, a variety of 9-halogenated o-carboranes and m-carboranes were obtained in good to excellent yields with broad tolerance of functional groups

Improved and Scalable Synthesis of [Et₄N][<i>closo</i>-1-CHB₉H₉]

The derivatives of the [closo-1-CHB9H9]− anion have attracted increasing attention in the fields of catalysis and materials exhibiting superionic conductivity. The Brellochs method is widely utilized to synthesize the derivatives of the [closo-1-CHB9H9]− anion. On the basis of this innovative method, we have further developed a facile method, which is rapidly scalable to 37 g, and its overall yield of [Et4N]­[closo-1-CHB9H9] is up to ca 80%. The facile synthetic method is straightforward without the isolation of the [Et4N]­[arachno-6-CH2B9H12] intermediate. The cation exchange for oxidation cluster closure to the [closo-2-CHB9H9]− anion is avoided; positional isomerism of [closo-2-CHB9H9]− to [closo-1-CHB9H9]− can be conducted without a solvent, and conversion is almost quantitative

One-Pot Synthesis of Iodo-Dibenzothiazines from 2‑Biaryl Sulfides

Herein, we report a metal-free and step-economic synthesis of iodo-dibenzothiazines from 2-biaryl sulfides under mild reaction conditions. The reaction involves sulfoximination of sulfides, intramolecular C–H amination, and iodization using cheap commercially available reagents. The products represent heterocyclic building blocks, readily modifiable by classical cross-coupling reactions

B(9)-OH‑<i>o</i>‑Carboranes: Synthesis, Mechanism, and Property Exploration

Herein, we present a chemically robust and efficient synthesis route for B(9)-OH-o-carboranes by the oxidation of o-carboranes with commercially available 68% HNO3 under the assistance of trifluoromethanesulfonic acid (HOTf) and hexafluoroisopropanol (HFIP). The reaction is highly efficient with a wide scope of carboranes, and the selectivity of B(9)/B(8) is up to 98:2. The success of this transformation relies on the strong electrophilicity and oxidizability of HNO3, promoted through hydrogen bonds of the Brønsted acid HOTf and the solvent HFIP. Mechanism studies reveal that the oxidation of o-carborane involves an initial electrophilic attack of HNO3 to the hydrogen atom at the most electronegative B(9) of o-carborane. In this transformation, the hydrogen atom of the B–H bond is the nucleophilic site, which is different from the electrophilic substitution reaction, where the boron atom is the nucleophilic site. Therefore, this is an oxidation–reduction reaction of o-carborane under mild conditions in which N(V) → N(III) and H(-I) → H(I). The derivatization of 9-OH-o-carborane was further examined, and the carboranyl group was successfully introduced to an amino acid, polyethylene glycol, biotin, deoxyuridine, and saccharide. Undoubtedly, this approach provides a selective way for the rapid incorporation of carborane moieties into small molecules for application in boron neutron capture therapy, which requires the targeted delivery of boron-rich groups