Ring-Closing Metathesis Dimerizations of Enynes and Deprotections of Propargyl Ethers Mediated by Carbene Ruthenium Complexes

Hahn, Dong-Woo,Byun, Dong-Min,Tae, Jinsung WILEY-VCH Verlag 2005 European journal of organic chemistry Vol.2005 No.1

<P>The ring-forming dimerizations of enynes were catalyzed by the first-generation carbene ruthenium complex, and the effects of the catalysts and ethylene gas were studied. The deprotection of propargyl ethers by the carbene ruthenium complexes is the first to be reported. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2005)</P> <B>Graphic Abstract</B> <P> <img src='wiley_img/1434193X-2005-2005-1-EJOC200400630-fig000.gif' alt='wiley_img/1434193X-2005-2005-1-EJOC200400630-fig000'> </P>

Unprecedented N-Inserted Disulfide Ligand Stabilized by Coordination to the Electropositive Co^III Center

Yoo, Houng Sik,Yoon, Jung Hee,Kim, Jae Il,Koh, Eui Kwan,Hong, Chang Seop WILEY-VCH Verlag 2008 European journal of inorganic chemistry Vol.2008 No.20

<P>The reaction of Co<SUP>II</SUP> and 2,2′-dipyridyldisulfide (PySSPy) in the presence of azide produced a peculiar monomeric complex [Co<SUP>III</SUP>(PyS)(PyS-N-SPy)(N<SUB>3</SUB>)] (1). In this reaction, redox chemistry takes place, which is associated mainly with the oxidation of Co<SUP>II</SUP> to Co<SUP>III</SUP> and the reduction of PySSPy. During the reaction, the azide ion decomposes and donates a nitrogen atom to PySSPy. The crystal structure of 1 provides evidence that the unusual, N-inserted ligand PyS-N-SPy can be stabilized through coordination to the electropositive Co<SUP>III</SUP> ion. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2008)</P> <B>Graphic Abstract</B> <P>The reaction of Co<SUP>II</SUP> and 2,2′-dipyridyldisulfide (PySSPy) in the presence of azide produced a monomeric complex [Co<SUP>III</SUP>(PyS)(PyS-N-SPy)(N<SUB>3</SUB>)] (1), which was characterized by means of UV/Vis, X-ray crystallography, XPS, and cyclic voltammetry. The unusual, N-inserted ligand PyS-N-SPy can be stabilized through coordination to the electropositive Co<SUP>III</SUP> ion. <img src='wiley_img/14341948-2008-2008-20-EJIC200800439-fig000.gif' alt='wiley_img/14341948-2008-2008-20-EJIC200800439-fig000'> </P>

Change in Supramolecular Networks through In Situ Esterification of Porphyrins

Chen, Wentong,Fukuzumi, Shunichi WILEY-VCH Verlag 2009 European journal of inorganic chemistry Vol.2009 No.36

<P>A series of porphyrins, M[TCPP-Et<SUB>4</SUB>] [M = Zn (1), Cu (2), and Ni (3); Et = CH<SUB>2</SUB>CH<SUB>3</SUB>; TCPP = meso-tetra(4-carboxyphenyl)porphyrin], M[TCPP-Me<SUB>4</SUB>] [M = Zn (4), Cu (5), and Co (6); Me = CH<SUB>3</SUB>], and two nonmetalated compounds, TCPP-Et<SUB>4</SUB> (7) and TCPP-Me<SUB>4</SUB>·H<SUB>2</SUB>O (8), were synthesized by solvothermal reactions and characterized by single-crystal X-ray diffraction. Compounds 1–3 feature an isolated structure with a planar macrocycle and an embedded metal-ion coordinating to four pyrrole nitrogen atoms. Compound 4 is characterized as a two-dimensional coordination polymer, and the zinc ion coordinates to four nitrogen atoms and two oxygen atoms. Compound 4 possesses a large void space (361 Å<SUP>3</SUP>), which corresponds to 14 % of the unit-cell volume. Compounds 5 and 6 are characteristic of an isolated motif with a four-coordinate metal ion and a saddle-distorted nonplanar porphyrin macrocycle. Nonmetalated compounds 7 and 8 also show an isolated structure with a planar macrocycle. For compounds 1–3 and 7, the TCPP is esterified with ethanol, while for compounds 4–6 and 8, the TCPP is esterified with methanol. The molecules in 1 and 6–8 are interconnected by hydrogen bonds and π–π interactions to yield 3D supramolecular networks, while in 2–5, 2D supramolecular motifs are formed. The reaction mechanism was explored. Esterification plays an important role in changing the properties of the compounds as well as in the formation of different structural motifs and supramolecular networks. The UV/Vis, FTIR, fluorescence, phosphorescence, and MALDI-TOF MS spectra, quantum yields, luminescence lifetimes, and cyclic voltammograms were also studied in detail.(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2009)</P> <B>Graphic Abstract</B> <P>Eight esterified TCPP compounds were successfully synthesized by solvothermal reactions and characterized. The reaction mechanism was investigated. Esterification plays a vital role in the properties, structural motifs and supramolecular networks. <img src='wiley_img/14341948-2009-2009-36-EJIC200900801-fig000.gif' alt='wiley_img/14341948-2009-2009-36-EJIC200900801-fig000'> </P>

Synthesis and Aqueous Colloidal Solutions of RE₂(OH)₅NO₃·nH₂O (RE = Nd and La)

Lee, Kyung-Hee,Byeon, Song-Ho WILEY-VCH Verlag 2009 European journal of inorganic chemistry Vol.2009 No.31

<P>A new, simple route leading to layered rare-earth hydroxy nitrates was developed. The pH-independent procedure uses ethanol containing alkali-metal hydroxide (KOH, RbOH, or CsOH) as a solvothermal medium. Two new, layered rare-earth hydroxy nitrates (LRHs), Nd<SUB>2</SUB>(OH)<SUB>5</SUB>NO<SUB>3</SUB>·nH<SUB>2</SUB>O and La<SUB>2</SUB>(OH)<SUB>5</SUB>NO<SUB>3</SUB>·nH<SUB>2</SUB>O, were prepared by this nonaqueous solvothermal reaction. Because the RE = Nd and La members have not yet been synthesized in an aqueous system, the successful synthesis of these compounds implies the completion of the RE<SUB>2</SUB>(OH)<SUB>5</SUB>NO<SUB>3</SUB>·nH<SUB>2</SUB>O (RE = rare earths) series. The typical properties of a layered structure was demonstrated by ready ion-exchange reactions between NO<SUB>3</SUB><SUP>–</SUP> and some organic anions such as decanoate, decanesulfonate, and decyl sulfate. In particular, the as-synthesized hydroxide from solvothermal reaction, where the alkali-metal nitrates are partially intercalated in the interlayer gallery, form an aqueous colloidal solution under ultrasonic treatment. Hydration of the LRHs intercalated with alkali-metal salts results in the formation of colloidal LRH suspensions in water. The colloidal character of the LRH solutions is supported by the Tyndall effect, TEM, and AFM images.(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2009)</P> <B>Graphic Abstract</B> <P>A new, simple route was developed to synthesize the complete rare-earth series of the RE<SUB>2</SUB>(OH)<SUB>5</SUB>NO<SUB>3</SUB>·nH<SUB>2</SUB>O family. The hydration of La<SUB>2</SUB>(OH)<SUB>5</SUB>NO<SUB>3</SUB>·nH<SUB>2</SUB>O and Nd<SUB>2</SUB>(OH)<SUB>5</SUB>NO<SUB>3</SUB>·nH<SUB>2</SUB>O synthesized by this nonaqueous solvothermal method yielded transparent aqueous colloidal solutions. <img src='wiley_img/14341948-2009-2009-31-EJIC200900635-fig000.gif' alt='wiley_img/14341948-2009-2009-31-EJIC200900635-fig000'> </P>

Systematic Electronic Control in Ambipolar Compounds Optimizes Their Photoluminescence Properties: Synthesis, Characterization, and Device Fabrication of Four-Coordinate Boron Compounds Containing an N,O-Chelating Oxazolylphenolate Ligand

Son, Ho-Jin,Han, Won-Sik,Wee, Kyung-Ryang,Chun, Ji-Yun,Choi, Kyu-Bum,Han, Su Jung,Kwon, Soon-Nam,Ko, Jaejung,Lee, Chongmok,Kang, Sang Ook WILEY-VCH Verlag 2009 European journal of inorganic chemistry Vol.2009 No.11

<P>A series of four-coordinate boron compounds of the type N,O-(OPh<SUP>OxZ</SUP>ArX)BPh<SUB>2</SUB> or N,O-(OPh<SUP>OxZ</SUP>NPh<SUB>2</SUB>)BPh<SUB>2</SUB> (5a–g) has been prepared by treating triphenylboron (TPB) with2-(4,4-dimethyl-4,5-dihydrooxazol-2-yl)-4-X-arylphenols(HOPh<SUP>OxZ</SUP>ArX; 4a–f) or 2-(4,4-dimethyl-4,5-dihydrooxazol-2-yl)-4-(4-diphenylamino)phenol (HOPh<SUP>OxZ</SUP>NPh<SUB>2</SUB>; 4g). A systematic change in the electronic structures is achieved in these compounds by incorporating electron-withdrawing (EW) and -donating (ED) groups [ArX (X = 4-cyano-, 2,4-difluoro-, 4-chloro-, phenyl, 4-methoxy-, and 4-dimethylaminophenyl) or NPh<SUB>2</SUB>] at the 4-position of the phenoxide. The absorption and emission maxima of the ED groups show a significant red-shift compared to those observed in the EW groups. This red-shift suggests that π-conjugation is effectively extended over the arylphenoxides and oxazoline moiety once the boron center has been plugged into the corresponding ligands. The gradual decrease observed in the bandgaps on going from EW to ED groups is found to be in agreement with the increase in oxidation potentials determined by the cyclic voltammetry (CV) experiments. In particular, a Hammet plot between the EW and ED substituents and oxidation potentials confirms the ground state electronic perturbation. Such alterations are attributed mainly to an elevation of the energy levels of the HOMOs), as further confirmed by a series of theoretical calculations on the frontier orbitals of each system. The ED group (-NPh<SUB>2</SUB>) substituted compound 5g shows a bipolar character due to intramolecular charge transfer in the complex, with the highest photoluminescence quantum yield being obtained in toluene. This new boron complex was found to function as an emitter in electroluminescence (EL) devices, with a maximum brightness of 2905 cd/m<SUP>2</SUP> at 13 V and a current efficiency of 1.63 cd/A at 6 mA/cm<SUP>2</SUP>, with a turn-on voltage of 4.3 V.(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2009)</P> <B>Graphic Abstract</B> <P>A series of electron-push and -pull aryl-substituted oxazolylphenolate ligands is synthesized and used to prepare boron compounds. The photophysical properties of these boron compounds are evaluated,and the corresponding EL properties studied through device fabrication by using them as emitting materials in a multilayer device. <img src='wiley_img/14341948-2009-2009-11-EJIC200900017-fig000.gif' alt='wiley_img/14341948-2009-2009-11-EJIC200900017-fig000'> </P>

Silver(I) and Copper(I) Coordination Polymers Based on Thiaoxa-Macrocycles

Kim, Hyun Jee,Song, Mi Ryoung,Lee, So Young,Lee, Jai Young,Lee, Shim Sung WILEY-VCH Verlag 2008 European journal of inorganic chemistry Vol.2008 No.22

<P>Two S<SUB>2</SUB>O<SUB>2</SUB>-macrocycles with different ring size (L<SUP>1</SUP>: 17- and L<SUP>2</SUP>: 18-membered) were synthesised and structurally characterised by X-ray analysis. Reactions of L<SUP>1</SUP> and L<SUP>2</SUP> with silver(I) salts (ClO<SUB>4</SUB><SUP>–</SUP> and NO<SUB>3</SUB><SUP>–</SUP>) afforded respective ligand- and/or anion-directed complexes 1–4 with different topologies; single-stranded 1D coordination polymer [AgL<SUP>1</SUP>(ClO<SUB>4</SUB>)(DMSO)]<SUB>n</SUB> (1), double-stranded 1D coordination polymer {[Ag<SUB>2</SUB>(L<SUP>1</SUP>)<SUB>2</SUB>(NO<SUB>3</SUB>)<SUB>2</SUB>]·DMSO}<SUB>n</SUB> (2), cyclic dimer [Ag<SUB>2</SUB>(L<SUP>2</SUP>)<SUB>2</SUB>(ClO<SUB>4</SUB>)<SUB>2</SUB>]·CH<SUB>2</SUB>Cl<SUB>2</SUB>·CH<SUB>3</SUB>OH (3) and 2D polymeric sheet [Ag(L<SUP>2</SUP>)NO<SUB>3</SUB>]<SUB>n</SUB> (4). Meanwhile, reactions of these two ligands with copper(I) iodide afforded 1D (5) and 2D (6a) coordination polymers linked with a rhomboid-type Cu–I<SUB>2</SUB>–Cu unit, respectively. The formation of such discrete and continuous supramolecular complexes is discussed in terms of discrimination of the anion effect, ligand flexibility as well as interligand π-π stacking interaction. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2008)</P> <B>Graphic Abstract</B> <P>Two analogous dithiamacrocycles (17- and 18-membered) are synthesised. Five coordination polymers and one metallo-cyclic dimer were obtained from the reactions of the macrocycles with the silver(I) and copper(I) salts. The versatility of results is discussed in relation to macrocyclic ring flexibility, anions and π-π stacking. <img src='wiley_img/14341948-2008-2008-22-EJIC200800284-fig000.gif' alt='wiley_img/14341948-2008-2008-22-EJIC200800284-fig000'> </P>

Synthesis of the Tetraketide Lactones from the Pikromycin Biosynthetic Pathway

Oh, Hong-Se,Yun, Ji-Suk,Nah, Ki-Hyun,Kang, Han-Young,Sherman, David H. WILEY-VCH Verlag 2007 European journal of organic chemistry Vol.2007 No.20

<P>Synthesis of tetraketide lactones 2 and 3, which are likely to be produced by a model pikromycin polyketide synthase (PKS), has been investigated. The tetraketide lactones with six-membered rings, 2a and 2b, were synthesized successfully by the asymmetric aldol reaction, allylation, and the Reformatsky reaction. The attempted synthesis of tetraketide lactones with eight-membered rings, 3a and 3b, led to the formation of the compounds 2a and 2b. The synthesis of another tetraketide lactone compounds 35 was attempted with the hope that introducing an additional methyl group would lead to a change in thermodynamic stability. However, it produced the corresponding tetraketide lactone 34 with a six-membered ring. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2007)</P> <B>Graphic Abstract</B> <P> <img src='wiley_img/1434193X-2007-2007-20-EJOC200700254-fig000.gif' alt='wiley_img/1434193X-2007-2007-20-EJOC200700254-fig000'> </P>

Ratiometric Fluorescence Sensing of Fluoride Ions by an Asymmetric Bidentate Receptor Containing a Boronic Acid and Imidazolium Group

Xu, Zhaochao,Kim, Sook Kyung,Han, Su Jung,Lee, Chongmok,Kociok-Kohn, Gabriele,James, Tony D.,Yoon, Juyoung WILEY-VCH Verlag 2009 EUROPEAN JOURNAL OF ORGANIC CHEMISTRY Vol.2009 No.18

<P>The synthesis of the first examples of anion receptors that utilize boron–fluoride interactions and (C–H)<SUP>+</SUP>···F<SUP>–</SUP>-type ionic hydrogen-bond interactions in the binding of F ions is reported herein. o-, m-, and p-Phenylboronic acids were linked to naphthoimidazolium through a methylene group. On the basis of fluorescence and <SUP>19</SUP>F NMR studies, we have confirmed that the addition of fluoride to a boron center occurs prior to the formation of (C–H)<SUP>+</SUP>···F<SUP>–</SUP>-type ionic hydrogen bond with the imidazolium moiety. More importantly, these investigations have demonstrated that only the receptor bearing the ortho-directed boron and imidazolium exhibits enhanced fluoride binding. The increased binding ability of the asymmetric bidentate receptor of ortho-boronic acid and imidazolium towards F<SUP>–</SUP> enables it to sense fluoride ions in a 95:5 CH<SUB>3</SUB>CN/HEPES aqueous solution. The fluorescence responses to different anions were also explored; the ortho-boron-imidazolium receptor displayed ratiometric fluorescence changes and a high selectivity towards fluoride ions over other anions (Cl<SUP>–</SUP>, Br<SUP>–</SUP>, CH<SUB>3</SUB>CO<SUB>2</SUB><SUP>–</SUP>, HSO<SUB>4</SUB><SUP>–</SUP>, and H<SUB>2</SUB>PO<SUB>4</SUB><SUP>–</SUP>).(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2009)</P> <B>Graphic Abstract</B> <P>An asymmetric bidentate receptor containing boronic acid and an imidazolium group can recognize F<SUP>–</SUP>, as evidenced by ratiometric fluorescence responses in aqueous solution. <img src='wiley_img/1434193X-2009-2009-18-EJOC200900120-fig000.gif' alt='wiley_img/1434193X-2009-2009-18-EJOC200900120-fig000'> </P>

Cu₂O Nanocube-Catalyzed Cross-Coupling of Aryl Halides with Phenols via Ullmann Coupling

Kim, Jee Young,Park, Ji Chan,Kim, Aram,Kim, A. Young,Lee, Hyun Ju,Song, Hyunjoon,Park, Kang Hyun WILEY-VCH Verlag 2009 European journal of inorganic chemistry Vol.2009 No.28

<P>Thermal and air-stable uniform Cu<SUB>2</SUB>O nanocubes were employed in the development of a gram-scale, one-pot polyol synthesis. Herein is reported an efficient cross-coupling reaction of aryl halides and phenols with a catalytic amount (0.1 mol-%) of Cu<SUB>2</SUB>O nanocubes as recyclable catalyst and Cs<SUB>2</SUB>CO<SUB>3</SUB> as the base in THF at 150 °C. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2009)</P> <B>Graphic Abstract</B> <P>An efficient cross-coupling reaction of aryl halides and phenol with 0.1 mol-% Cu<SUB>2</SUB>O nanocubes as recyclable catalyst and Cs<SUB>2</SUB>CO<SUB>3</SUB> as the base in THF at 150 °C is reported. The process is simple and allows the formation of a diverse range of diaryl ethers in excellent yields. <img src='wiley_img/14341948-2009-2009-28-EJIC200900730-fig000.gif' alt='wiley_img/14341948-2009-2009-28-EJIC200900730-fig000'> </P>

Preparation of Mesoporous Silica and Carbon Materials with Multilength-Scale Pores and Hydrogen Sorption Application

Kwon, Tae-Hwan,Jung, Suhyun,Kim, Hee-Jin,Park, Seongsoon,Kim, Sung-Jin,Huh, Seong WILEY-VCH Verlag 2009 European journal of inorganic chemistry Vol.2009 No.19

<P>A facile method was developed for the preparation of bimodal mesoporous siliceous materials with nanostructured pores in which a cationic organic template, n-hexadecyltrimethylammonium hydroxide, was employed as a base catalyst as well as a mesopore structure-directing agent during the slow condensation of tetraethoxysilane. It was possible to alter the pore orientations of smaller pores by adding neutral auxiliary templates such as Brij76 and P123. A series of biomodal mesoporous carbons was also obtained from the bimodal mesoporous silica materials through a nanocasting process. The resulting bimodal mesoporous carbons exhibited decent hydrogen uptake values at 77 K. The maximum hydrogen uptake was 1.33 wt.-% for the sample having the narrowest pores, while keeping a relatively large pore volume. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2009)</P> <B>Graphic Abstract</B> <P>A simple preparation method of various bimodal mesoporous silica and carbon materials with interesting nanostructures was developed. Their hydrogen uptake abilitieswere investigated at 77 K. The sample with small pores and a large pore volume showed enhanced hydrogen sorption ability. <img src='wiley_img/14341948-2009-2009-19-EJIC200900153-fig000.gif' alt='wiley_img/14341948-2009-2009-19-EJIC200900153-fig000'> </P>