Intermolecular Radical Carbofluorination of Non‐activated Alkenes

The Meerwein arylation has recently become an even more powerful tool for the functionalization of alkenes. Besides the attachment of an aryl group, radical reactions of this type allow the introduction of several different heteroatoms and a broad variety of alkenes are meanwhile tolerated as substrates. Closing a long‐standing gap of the methodology, this communication describes the first intermolecular Meerwein‐type carbofluorination. In metal‐free reactions, arylalkyl fluorides were obtained from arylhydrazines and alkenes with Selectfluor acting as oxidant and as radical fluorine source.     

Synthesis of β-Ketoiminato Copper(II) Complexes and Their Use in Copper Deposition

The template synthesis of ethylenediamine ( 1 ) with 2-acetylcyclopentanone ( 2 ) and [Cu(OAc)₂ · H₂O] ( 5 ) produced [Cu(1-(2-cC₅H₆(O))C(Me)NCH₂)₂)] ( 6 ) in 82 % yield. Reaction of 5 with bis(benzoylacetone)diethylenetriamine ( 7 , = L H)^[1] gave [Cu(μ-OAc)( L )(H₂O)]₂ ( 8 ). The solid-state structures of 6 and 8 were determined confirming that 8 possesses intra- and intermolecular hydrogen bonds resulting in a dimer formation. The thermal behavior of 6 – 8 was studied by TG and TG-MS. Under oxygen CuO was formed, whereas under Ar Cu/Cu₂O ( 6 ) or Cu ( 8 ) was obtained. Complex 6 was used as CVD precursor for Cu and Cu-oxide deposition (substrate temp., 400–500 °C, N₂, 60 mL · min^–1; O₂, 60 mL · min^–1; pressure, 0.87–1.5 mbar). The as-obtained deposits show separated particles of different appearance at the substrate surface as evidenced by SEM. Non-volatile 8 was applied as spin-coating precursor for Cu and CuO formation [conc. 0.25 mol · L^–1; volume 0.2 mL; 3000 rpm; depos. time 2 min; heating rate 50 K · min^–1; holding time 60 min (Ar), 120 min (air) at 800 °C]. The samples on silicon consist of granulated particles (Ar) or are non-dense with a grainy topography (air). EDX and XPS measurements confirmed the formation of Cu (Ar) or CuO (O₂) with up to 13 mol-% C impurity.     

RuII and RuIII Chloronitrile Complexes: Synthesis,Reaction Chemistry,Solid State Structure,and (Spectro)Electrochemical Behavior

The synthesis of [Ti₆O₄(OiPr)₈(O₂CPh)₈] ( 3 ) and [RuCl(N≡CR)₅][RuCl₄(N≡CR)₂] ( 4a , R = Me; 4b , R = Ph), [Ru(N≡CPh)₆][RuCl₄(N≡CPh)₂] ( 5 ) and [H₃O][RuCl₄(N≡CMe)₂] ( 7a ) is discussed. Crystallization of 5 from CH₂Cl₂ gave trans-[RuCl₂(N≡CPh)₄] ( 6 ). The solid-state structures of 3 , 4a , b , 5 , 6 and 7a are reported. Complex 4b forms a 3D network, while 6 displays a 2D structure, due to π-interactions between the benzonitrile ligands. The (spectro)electrochemical behavior of 4a , b and 6 was studied at 25 and –72 °C and the results thereof are compared with [NEt₄][RuCl₄(N≡CMe)₂] ( 7b ) and [RuCl(N≡CPh)₅][PF₆] ( 8 ). The electrochemical response of the cation and the anion in 4a , b are independent from each other. [RuCl(N≡CR)₅]⁺ possesses one reversible Ru^II/Ru^III process. However, [RuCl₄(N≡CMe)₂]^– was shown to be prone to ligand exchange and disproportionation upon formation of either a Ru^IV and Ru^II species at 25 °C, while at –72 °C the rapid conversion of the electrochemically formed species is hindered. In situ IR and UV/Vis/NIR studies confirmed the respective disproportionation reaction products of the aforementioned oxidation and reduction, respectively.     

An Arylazopyrazole‐Based N‐Heterocyclic Carbene as a Photoswitch on Gold Surfaces: Light‐Switchable Wettability,Work Function,and Conductance

A novel photoresponsive and fully conjugated N‐heterocyclic carbene (NHC) has been synthesized that combines the excellent photophysical properties of arylazopyrazoles (AAPs) with an NHC that acts as a robust surface anchor (AAP‐BIMe). The formation of self‐assembled monolayers (SAMs) on gold was proven by ToF‐SIMS and XPS, and the organic film displayed a very high stability at elevated temperatures. This stability was also reflected in a high desorption energy, which was determined by temperature‐programmed SIMS measurements. E‐/Z‐AAP‐BIMe@Au photoisomerization resulted in reversible alterations of the surface energy (i.e. wettability), the surface potential (i.e. work function), and the conductance (i.e. resistance). The effects could be explained by the difference in the dipole moment of the isomers. Furthermore, sequential application of a dummy ligand by microcontact printing and subsequent backfilling with AAP‐BIMe allowed its patterning on gold. To the best of our knowledge, this is the first example of a photoswitchable NHC on a gold surface. These properties of AAP‐BIMe@Au illustrate its suitability as a molecular switch for electronic devices.     

Fast and efficient immunoaffinity column cleanup and liquid chromatography–tandem mass spectrometry method for the quantitative analysis of aflatoxins in baby food and feeds

An ultra high performance liquid chromatography‐tandem mass spectrometric method has been developed for the highly sensitive and selective determination of regulated aflatoxins. The extraction of aflatoxins from baby food matrices were performed using liquid–liquid extraction procedure followed by immunoaffinity column cleanup. The higher sensitivity for the determination of target aflatoxins was fulfilled by applying a preconcentration step with immunoaffinity columns after acetonitrile–water extraction. The enhanced selectivity was attained with the triple quadrupole mass analyzer operated in electrospray positive ionization mode. Method validation was tested in five different baby food matrices by recovery experiments. Satisfactory recoveries, between 92 and 103%, with relative standard deviations lower than 8% were achieved in all the tested matrices. The proposed method was found to be specific as no interference peaks were observed for blank samples. The limit of detection of the method was found to be in the range of 0.003–0.008 ng/mL. The validated method was fruitfully applied to the screening of aflatoxins in baby foods and feeds sample retailed in local markets of Riyadh, Saudi Arabia. The obtained levels of all analyzed aflatoxins were below the regulation limits set by European Agency.     

(Diazoalkyl)Phosphoranes from [4 + 1]-cycloadditions of tetrahalo-orthobenzoquinones to (diazoalkyl)phosphanes [1]

The (diazoalkyl)phosphanes 4a–e undergo [4 + 1]-cycloaddition reactions with the tetrahalo-orthobenzoquinones 5a,b to furnish the previously unknown (diazoalkyl)phosphoranes 6a–h . The structure of product 6h has been investigated by X-ray crystallography.     

行和列和为常量的(0,1)-矩阵的计数

Let fs,t(m,n) be the number of (0,1) - matrices of size m x n such that each row has exactly s ones and each column has exactly t ones (sm = nt). How to determine fs,t(m,n)? As R. P. Stanley has observed (Enumerative CombinatoricsⅠ(1997), Example 1.1.3), the determination of fs,t(m, n) is an unsolved problem, except for very small s, t. In this paper the closed formulas for f2,2(n,n), f3,2(m,n), f4,2(m,n) are given. And recursion formulas and generating functions are discussed.