From oxides of internal perfluoroolefins to fluorocontaining camphor thiazolinylhydrazones

The reaction of oxides of internal trans- and cis-perfluoroolefins with (1S, 4S)- or racemic camphor thiosemicarbazone leads to the formation of trans- and cis-isomers of (1S, 4S)- or racemic camphor 5′-fluoro-4′-hydroxy-4′,5′-di(perfluoroalkyl)-1′,3′-thiazolinyl-2′-hydrazones, respectively. Unsymmetrical dodecafluoro-2,3-epoxyhexane yields a mixture of regioisomeric hydrazones. The molecular structure of the trans-isomer of (1S, 4S)-camphor 5′-fluoro-4′-hydroxy-4′,5′-bis(trifluoromethyl)-1′,3′-thiazolinyl-2′-hydrazone has been established by X-ray crystallography. The quite rare example of cocrystallization of two diastereomers of the latter in homochiral crystal (sp. group P2₁) has been revealed.     

Mixed nitrosyl/phosphinidene and nitrene/phosphinidene clusters of ruthenium

Reaction of the aminophosphinidene complex [Ru5(CO)15(mu 4-PNPri2)] 1 with [PPN][NO2] (PPN = Ph3P=N=PPh3) led to the mixed nitrosyl/phosphinidene cluster complex [PPN][Ru5(CO)13(mu-NO)(mu 4-PNPri2)] 2 which is transformed into the novel nitrene/phosphinidene cluster [Ru5(CO)10(mu-CO)2(mu 3-CO)(mu 4-NH)(mu 3-PNPri2)] 3 via treatment with triflic acid.     

Reagents for Selective Fluoromethylation: A Challenge in Organofluorine Chemistry

The introduction of a monofluoromethyl moiety has undoubtedly become a very important area of research in recent years. Owing to the beneficial properties of organofluorine compounds, such as their metabolic stability, the incorporation of the CH₂F group as a bioisosteric substitute for various functional groups is an attractive strategy for the discovery of new pharmaceuticals. Furthermore, the monofluoromethyl unit is also widely used in agrochemistry, in pharmaceutical chemistry, and in fine chemicals. The problems associated with climate change and the growing need for environmentally friendly industrial processes mean that alternatives to the frequently used CFC and HFBC fluoromethylating agents (CH₂FCl and CH₂FBr) are urgently needed and also required by the Montreal Protocol. This has recently prompted many researchers to develop alternative fluoromethylation agents. This Minireview summarizes both the classical and new generation of fluoromethylating agents. Reagents that act via electrophilic, nucleophilic, and radical pathways are discussed, in addition to their precursors.     

Controlling Gas Selectivity in Molecular Porous Liquids by Tuning the Cage Window Size

Control of pore window size is the standard approach for tuning gas selectivity in porous solids. Here, we present the first example where this is translated into a molecular porous liquid formed from organic cage molecules. Reduction of the cage window size by chemical synthesis switches the selectivity from Xe‐selective to CH₄‐selective, which is understood using ¹²⁹Xe, ¹H, and pulsed‐field gradient NMR spectroscopy.     

Cobalt‐Catalyzed Cross‐Coupling of Functionalized Alkylzinc Reagents with (Hetero)Aryl Halides

A combination of 10 % CoCl₂ and 20 % 2,2′‐bipyridine ligands enables cross‐coupling of functionalized primary and secondary alkylzinc reagents with various (hetero)aryl halides. Couplings with 1,3‐ and 1,4‐substituted cycloalkylzinc reagents proceeded diastereoselectively leading to functionalized heterocycles with high diastereoselectivities of up to 98:2. Furthermore, alkynyl bromides react with primary and secondary alkylzinc reagents providing the alkylated alkynes.     

Metal-organic frameworks incorporating Cu3(mu3-OH) clusters

Interaction of 4,4-bi(1,2,4-triazole) (btr) with copper(II) chloride (bromide) in aqueous or aqueous alcohol media led to a series of coordination polymers featuring the formation of mu 3-hydroxotricopper(II) clusters and their integration into 3D frameworks. These unprecedented structures originate in the propagation of trigonal hydroxotricopper(II) clusters bridged by tri- or tetradentate organic ligands. Complex [{Cu3(mu3-OH)}{Cu3(mu3-O)}(mu4-btr)3(H2O)4(OH)2Cl6]Cl.0.5H2O adopts a structure of SrSi2 topology, with eight-fold interpenetration of the coordination frameworks. The structure of [{Cu3(mu3-OH)}2(mu3-btr)6(mu4-btr)(mu-X)X4]X5.nH2O (X = Br, n = 6; X = Cl, n = 8) involves 2D coordination layers [{Cu3(mu3-OH)}(mu3-btr)3]n with an exceptional (3,6)-net topology, which are cross-linked by tetradentate btr ligands and bridging chloride (bromide) ions.     

Acetonitrile-facilitated reductive dimerization of TCNE to octacyanobutanediide, [C4(CN)8]2-, by Iron(II) chloride

The redox properties of MCl2 (M=Mn, Fe, Co) acetonitrile solvates were electrochemically and spectroscopically characterized. The three voltammogram waves at 0.86, 0.48, and 0.21 V versus SCE for FeCl(2) dissolved in MeCN are assigned as one-electron reduction potentials for [Fe(II)Cl(x)(NCMe)4-x]2-x (1相似文献