- A comparative study of third-order nonlinear optical properties of silver phenylacetylide and related compounds via ultrafast optical kerr effect measurements
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A comparative study of the third-order nonlinear optical properties, via the newly developed heterodyned optical Kerr effect (OHD-OKE) measurements, of silver phenylacetylide and related compounds is reported. [AgC≡CC6H5]n (1) was found to exhibit efficient third-order nonlinear optical susceptibility X(3) of 2.4 × 10-14 esu, and second hyperpolarizability γ of 9.07 × 10-32 esu. These results are compared with those of two related silver phenylacetylide compounds, namely, a double salt, (silver phenylacetylide)·(silver tert-butylthiolate) [AgC≡CC6H5·AgS (t-C4H9)]n complex (2), and a cluster, triphenylphosphine silver phenylacetylide tetramer, [(C6H5)3PAgC≡ CC6H5]4 (3), as well as that of the related organic polymer polyphenylacetylene (4). These four compounds represent different types of phenylacetylide derivatives: 1 is an organometallic polymer, 2 a polymeric double salt, 3 a discrete metal cluster, and 4 an organic polymer. It was found that the third-order optical nonlinear response was enhanced by the incorporation of silver d electrons into the delocalized conjugated organic π system, and its magnitude is highly dependent upon the extent of the π delocalization. Specifically, the relative magnitudes of X(3) and γ follow the order silver phenylacetylide polymer (1) > (silver phenylacetylide)·(silver tert-butylthiolate) double salt (2) > polyphenylacetylene polymer (4) > tetrameric (triphenylphosphine silver phenylacetylide)4 cluster (3). The observed trend may be attributed to the decreasing length of π conjugation. It is interesting to note that the incorporation of Ag(I) into the polymeric framework of polyphenylacetylene enhances the X(3) by 25-fold for the same degree of polymerization (n = 7). The signs of X(3) and γ, which are related to the response mechanisms, were found to be solvent dependent.
- Teo,Xu,Zhong,He,Chen,Qian,Deng,Zou
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- Monocyclometalated gold(III) monoaryl complexes - A new class of triplet phosphors with highly tunable and efficient emission properties
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Highly tunable and rich phosphorescent emission properties based on the stable monocyclometalated gold(III) monoaryl structural motif are reported. Monochloro complexes of the type cis-[(N^C)Au(C6H2(CF 3)3)(Cl)]
- Szentkuti, Alexander,Bachmann, Michael,Garg, Jai Anand,Blacque, Olivier,VenKatosan, Koushik
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- Anion-Templated Nanosized Silver Alkynyl Clusters: Cluster Engineering and Solution Behavior
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Assembly of nanosized polynuclear metal clusters from simple building blocks usually involves complicated self-organization processes and thus is a long-standing challenge. Here, we demonstrate the controllable assembly, single-crystal structures and solution behaviors of four molecular assemblies based on nanosized silver alkynyl clusters, formulated as {[(CrO4)2Cl@Ag42(PhC≡C)34(CF3COO)2]?CF3COO} (1), {(NH4)[(CrO4)2Cl@Ag42(PhC≡C)34(CrO4)(H2O)2]?2BF4?CH3OH}n (2), [(CrO4)@Ag22(PhC≡C)16(CF3SO3)4]n (3), and {[(CrO4)2@Ag31(PhC≡C)22(CF3SO3)4]?CF3SO3?2CH3OH?H2O}n (4). In the presence of concomitant CrO42? and Cl? templates, we could isolate a discrete cluster 1 and a polymeric chain-like compound 2 by using different silver salts. Both 1 and 2 have a similar 42-metallic cage, which traps two CrO42? and one Cl? as anion templates. Using sole CrO42? template, 3 and 4 were simultaneously isolated in a one-pot reaction. Both of them are 1D chain structures based on single CrO42? templated Ag18 and double CrO42? templated Ag30 clusters, respectively. HR-ESI-MS was used to study the solution behaviors of 1–4. This work has the following purposes: i) it presents the cluster engineering concept used in the assembly of polynuclear silver alkynyl clusters; ii) it exemplifies template effects from hetero and homo anions; and iii) it provides a controllable way to achieve assembly of silver alkynyl clusters.
- Zhang, Shan-Shan,Su, Hai-Feng,Wang, Zhi,Wang, Lina,Zhao, Quan-Qin,Tung, Chen-Ho,Sun, Di,Zheng, Lan-Sun
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- Cyclopentadienyl-ruthenium and -osmium chemistry. XXXII. Some complexes containing tertiary phosphites: X-ray structures of RuCl2(η-C5H5) and of two isomers of RuCPh=C(CN)2>2(η-C5H5)
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Exchange of tertiary phosphites for PPh3 in RuCl(PPh3)2(η-C5H5) afforded RuCl2(η-C5H5) (R3=Me3, (CH2CF3)3, (CH2)3CEt).Conventional reactions of the P(OMe)3 complex afforded RuX2(η-C5H5) (X=H, C(CO2Me)=CH(CO2Me), SnCl3, C2Ph, *
- Bruce, Michael I.,Cifuentes, Marie P.,Snow, Michael R.,Tiekink, Edward R. T.
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- An Alkynyl-Stabilized Pt5Ag22 Cluster Featuring a Two-Dimensional Alkynyl–Platinum “Crucifix Motif”
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The “staple motif” has been widely applied to depict and predict the structures of thiolate or alkynyl-protected gold nanoclusters. By contrast, the composition, dimensions, configuration, and functionality of the platinum-ligand motif has remained completely unknown. Herein, we report the synthesis and crystal structure of a novel luminescent Pt5Ag22(C≡CPh)32 (1) cluster, in which two-dimensional and two-functional alkynyl–platinum “crucifix motif” was observed. Such a crucifix motif with one Pt center and four alkynyl groups in the same plane acts as a two-dimensional unit in the cluster and functions as both a protective cover and an intermediate joint.
- Shen, Hui,Mizuta, Tsutomu
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- A practical and efficient method for late-stage deuteration of terminal alkynes with silver salt as catalyst
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A practical and efficient H/D exchange method for selective deuteration of terminal alkynes was disclosed. The reaction was simply performed with CF3COOAg as catalyst at room temperature, affording products with high level of deuterium incorporation. The excellent site-selectivity and promising functional group tolerance of this protocol enabled deuteration of pharmaceuticals and nature product derivatives.
- Wu, Ding-Chuan,Bai, Jing-Wen,Guo, Lei,Hu, Guang-Qi,Liu, Kai-Hui,Sheng, Fei-Fei,Zhang, Hong-Hai,Sun, Zheng-Yi,Shen, Kang,Liu, Xiang
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supporting information
(2021/02/20)
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- AgN3-Catalyzed Hydroazidation of Terminal Alkynes and Mechanistic Studies
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The hydroazidation of alkynes is the most straightforward way to access vinyl azides-versatile building blocks in organic synthesis. We previously realized such a fundamental reaction of terminal alkynes using Ag2CO3 as a catalyst. H
- Bi, Xihe,Cao, Shanshan,Ji, Qinghe,Li, Huaizhi,Pang, Maolin,Yuan, Haiyan,Zhang, Jingping
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supporting information
p. 7083 - 7091
(2020/05/14)
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- N-Alkynylthio Phthalimide: A Shelf-Stable Alkynylthio Transfer Reagent for the Synthesis of Alkynyl Thioethers
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A new kind of electrophilic alkynylthiolating reagent, called N-alkynylthio phthalimide, is designed and synthesized herein. This electrophilic sulfenylating reagent can be easily prepared in three steps from commercially available phthalimide and corresp
- Gao, Wen-Chao,Shang, Yu-Zhu,Chang, Hong-Hong,Li, Xing,Wei, Wen-Long,Yu, Xin-Zhang,Zhou, Rong
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supporting information
p. 6021 - 6024
(2019/08/20)
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- One-pot synthesis of 2,4-disubstituted quinolines via silver-catalyzed three-component cascade annulation of amines, alkyne esters and terminal alkynes
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Described herein is a new and general method for one-pot synthesis of 2,4-disubstituted quinolines via silver-catalyzed [3 + 1 + 2] annulation of simple amines, alkyne esters and terminal alkynes. The versatile transformation might initiate with the facil
- Li, Yunlan,Zhang, Qiurui,Xu, Xuefeng,Zhang, Xu,Yang, Yurong,Yi, Wei
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supporting information
p. 965 - 970
(2019/03/13)
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- Organometallic Reactivity of [Silver(I)(Pyridine-Containing Ligand)] Complexes Relevant to Catalysis
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Silver(I) complexes of pyiridine-containing macrocyclic ligands (Pc-L) have already been demonstrated as active catalysts for some domino and multicomponent reactions. Here, we report new chiral [AgI(Pc-L)] cationic complexes that have been synthesized and fully characterized, including structural determination by single-crystal X-ray diffraction. The complexes show a rich coordination chemistry, demonstrating both the σ-philic (alcohol and nitrile coordination) and the π-philic (alkyne coordination) nature of silver. The η2 coordination mode of the naphthyl pendant arm of the ligands on silver has been observed in solution by NMR spectroscopic experiments. 2D NMR spectroscopy revealed the presence of positive cross peaks resulting from rotational processes and the rate of rotation was measured by using 2D exchange spectroscopy (EXSY).
- Pedrazzini, Tommaso,Pirovano, Paolo,Dell'Acqua, Monica,Ragaini, Fabio,Illiano, Pasquale,Macchi, Piero,Abbiati, Giorgio,Caselli, Alessandro
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supporting information
p. 5089 - 5098
(2015/11/03)
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- Cobalt(II)-catalyzed electrophilic alkynylation of 1,3-dicarbonyl compounds to form polysubstituted furans via π-π Activation
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Polysubstituted furans were obtained with excellent yields via the electrophilic alkynylation of 1,3-dicarbonyl compoundsws with phenyl- or ester-substituted brominated alkynes. The reaction is catalyzed by the inexpensive and readily available catalyst, cobalt(II) chloride, and has a wide substrate scope. The C(sp)-C(sp3) coupling occurs under mild conditions with short reaction times and does not require an inert atmosphere or ligands. It is proposed that the reaction proceeds through a chelation complex of cobalt(II) with the deprotonated 1,3-dicarbonyl compound.
- Roslan, Irwan Iskandar,Sun, Jiulong,Chuah, Gaik-Khuan,Jaenicke, Stephan
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supporting information
p. 719 - 726
(2015/03/18)
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- Silver-Mediated Selective Oxidative Cross-Coupling between C-H/P-H: A Strategy to Construct Alkynyl(diaryl)phosphine Oxide
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(Formula Presented) A direct oxidative cross-coupling between terminal alkynes and secondary phosphine oxides was developed. This approach provides an efficient way to construct alkynyl di(phenyl) phosphine oxides from basic materials, and in this process
- Wang, Tao,Chen, Songtao,Shao, Ailong,Gao, Meng,Huang, Yangfei,Lei, Aiwen
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p. 118 - 121
(2015/07/28)
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- Oxidative cross-coupling/cyclization to build polysubstituted pyrroles from terminal alkynes and β-enamino esters
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A novel silver-mediated highly selective synthesis of polysubstituted pyrroles by the C-H/C-H oxidative cross-coupling/cyclization of terminal alkynes with β-enamino esters has been developed. This protocol represents a simple, efficient and selective way to construct polysubstituted pyrroles in good yields from basic chemical materials.
- Ke, Jie,He, Chuan,Liu, Huiying,Li, Mengjun,Lei, Aiwen
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supporting information
p. 7549 - 7551
(2013/08/23)
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- Silver-mediated cycloaddition of alkynes with CF3CHN 2: Highly regioselective synthesis of 3-trifluoromethylpyrazoles
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Silver screen: The title reaction provides a convenient and efficient method for the construction of 5-substituted 3-trifluoromethylpyrazoles under mild reaction conditions. By using this protocol, the marketed drug Celecoxib (antiarthritic) could be easily synthesized (see scheme; DMF=N,N- dimethylformamide). Copyright
- Li, Feng,Nie, Jing,Sun, Long,Zheng, Yan,Ma, Jun-An
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supporting information
p. 6255 - 6258
(2013/07/05)
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- Synthesis of pyrroles by click reaction: Silver-catalyzed cycloaddition of terminal alkynes with isocyanides
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Just click with silver: Pyrroles are prepared by the co-cyclization of terminal alkynes and isocyanides in a silver-catalyzed click reaction. This route represents an extremely simple, efficient, and atom-economic approach to substituted pyrroles in good yields with high selectivity, thus complementing the click method for the rapid formation of multifunctional heterocycles. Copyright
- Gao, Meng,He, Chuan,Chen, Hongyi,Bai, Ruopeng,Cheng, Ben,Lei, Aiwen
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supporting information
p. 6958 - 6961
(2013/07/25)
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- Heteroaromatic imidazo[1,2-a]pyridines synthesis from C-H/N-H oxidative cross-coupling/cyclization
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A novel silver-mediated highly selective C-H/N-H oxidative cross-coupling/cyclization between 2-aminopyridines and terminal alkynes has been demonstrated. This approach provided a simple way to construct heteroaromatic imidazo[1,2-a]pyridines. By using this protocol, the marketed drug zolimidine (antiulcer) could be synthesized easily.
- He, Chuan,Hao, Jing,Xu, Huan,Mo, Yiping,Liu, Huiying,Han, Juanjuan,Lei, Aiwen
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supporting information
p. 11073 - 11075,3
(2012/12/12)
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- Heteroaromatic imidazo[1,2-a]pyridines synthesis from C-H/N-H oxidative cross-coupling/cyclization
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A novel silver-mediated highly selective C-H/N-H oxidative cross-coupling/cyclization between 2-aminopyridines and terminal alkynes has been demonstrated. This approach provided a simple way to construct heteroaromatic imidazo[1,2-a]pyridines. By using this protocol, the marketed drug zolimidine (antiulcer) could be synthesized easily.
- He, Chuan,Hao, Jing,Xu, Huan,Mo, Yiping,Liu, Huiying,Han, Juanjuan,Lei, Aiwen
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supporting information
p. 11073 - 11075
(2013/01/15)
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- CYCLOMETALATED AU(III) COMPLEXES SUITABLE FOR ELECTROLUMINESCENT DEVICES
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A process for the preparation of monocyclometalated Au(III) complexes, cis- [(N∧C)AuL1L2] and czs-[(N∧C)AuL1AL2] represented by generic chemical formulae la and lb respectively with ligands
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Page/Page column 22
(2012/05/31)
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- Electrochemical generation of silver acetylides from terminal alkynes with a Ag anode and integration into sequential Pd-catalysed coupling with arylboronic acids
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An electro-oxidative method for generating silver acetylides from acetylenes with a Ag anode was developed. The reaction could be integrated into a Pd-catalysed electrochemical Sonogashira-type reaction. In the presence of the catalytic amount of Pd(OAc)2 and 4-BzO-TEMPO, electro-generated silver acetylides reacted immediately with arylboronic acids to afford the corresponding coupling adducts in high yields.
- Mitsudo, Koichi,Shiraga, Takuya,Mizukawa, Jun-Ichi,Suga, Seiji,Tanaka, Hideo
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p. 9256 - 9258
(2011/02/22)
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- Synthese von [cis-(bipy)Pt(CCPh)2]AgFBF3 und dessen Reaktionsverhalten gegenueber Lewis-Basen; die Festkoerperstruktur von cis-(bipy)Pt(CCPh)2 und [(bipy)Pt(CCPh)(PPh3)]BF4
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The synthesis of the heterobimetallic platinum(II)-silver(I) complex {cis-(CCPh)2}AgFBF3 (3) in which the respective transition metals are bridged by ?- and ?-bound phenylacetylides, succeeds by the reaction of cis-[Pt](CCPh)2 {[Pt]=(bipy')Pt, bipy'=4,4'-dimethyl-2,2'-bipyridine} (1) with equimolar amounts of [AgBF4] (2). The reaction chemistry towards different Lewis-bases L (L=tetrahydrofuran, NR3, PPh3) is reported. Although 3 reacts with L to give coordination adducts of general type [{cis-[Pt](CCPh)2}AgL]BF4 in which the Lewis-base L is datively bound to the silver(I) ion, such a complex could only be isolated and characterised when L resembles PPh3 (4). All other Lewis-bases L are forming reversible adducts, which are only stable, when an excess of L is used. While [{cis-[Pt](CCPh)2}Ag(PPh3)]BF4 (5) is stable in the solid-state, it appeared that in solution it rearranges to produce the mononuclear, ionic platinum(II) complex {[Pt](CCPh) (PPh3)}BF4 (6) along with [AgCCPh] (8). The result of the X-ray structure analysis of 1 and 6 is reported. Complex 1 crystallises in the monoclinic space group C2/c with following cell parameters: a=19.3538(3), b=13.5356(3), c=8.9716(2) Angstroem, β=108.540(1)deg, V=2228.27(8) Angstroem3, Z=4 and δ=1.734 g mol-1. Complex 6 crystallises in the monoclinic space group P21/n with a=9.0321(1), b=22.8014(4), c=15.6304(3) Angstroem, β=100.2414(7)deg, V=3167.71(9) Angstroem3, Z=4 and δ=1.739 g mol-1. In both complexes a square-planar environment around the d8-configurated platinum(II) ion is typical. Each complex features a chelate-bound bipy' group. To reach the coordination number four, two PhCC ligands (1) or one phenylacetylide and a PPh3 group (6) are ?- or datively bound to the platinum atom.
- Lang, H.,Villar, A. del,Walfort, B.,Rheinwald, G.
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p. 155 - 162
(2007/10/03)
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- Synthesis of novel platinum-silver and platinum-copper complexes with bridging alkynyl ligands
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The study of the reactivity of CR)8> M = Ag or Cu; R = Ph or tBu) towards different neutral and anionic ligands is reported.This study reveals that reactions of the phenylacetylide derivatives CPh)8> with anionic, X- (X = Cl or Br) or neutral donors (CNtBu or py) in a molar ratio 1:4 (M/donor ratio 1:1) yield the trinuclear anionic (NBu4)2CPh)4>(MX)2> (M = Ag or Cu, X = Cl or Br) or neutral CPh)4>(AgL)2> (L = CNtBu or py) complexes, respectively.The crystal structure of (NBu4)2CPh)4>(CuBr)2>(4) shows that the anion is formed by a dianionic Pt(CCPh)4 fragment and two neutral CuBr units joined through bridging alkynyl ligands.All the alkynyl groups are ? bonded to Pt and η2-coordinated to a Cu atom which have an approximately trigonal-planar geometry.By contrast, similar reactions with CtBu)8> (molar ratio M/donor 1:1) afford hexanuclear dianionic (NBu4)2CtBu)8X2> or neutral CtBu)8Py2>.Only by treatment with a large excess of Br- (molar ratio M/Br- 1:2) are the trinuclear complexes (NBu4)2CtBu)4>(MBr)2> (M = Ag, Cu) obtained.Attempted preparations of analogous complexes with phosphines (L' = PPh3 or PEt3) by reactions of CR)8> with L' leads to displacement of alkynyl ligands from platinum and formation of neutral mononuclear complexes CR)2L'2>. Keywords: Platinum; Silver; Alkynyl; Copper; Polynuclear; X-ray diffraction
- Fornies, J.,Lalinde, E.,Martin, A.,Moreno, M.T.
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p. 179 - 188
(2007/10/02)
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- Syntheses and reactivity of acetylide-containing clusters of Group 1B metals. VIII. Preparation, characterization and possible structure of a novel pentanuclear trimetallic cluster -. Reactions of pentanuclear and trinuclear acetylide complexes
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The novel pentanuclear trimetallic cluster - has been prepared by the reactions of - with a mixture of gold phenylacetylide and silver phenylacetylide, of - with n>, or of - with n>.Its possible structure is discussed.The conversion of the pentanuclear clusters - and - into the high polynuclearity trimetallic cluster - and of - into the complex - is described.The reactions of - with PPh3, P(OMe)3, and CuCl, and those of 2- with n>, a mixture of n> and n>, and CuCl are reported.
- Abu-Salah, Omar M.,Al-Ohaly, Abdel Razzak A.,Mutter, Ziad F.
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p. 267 - 273
(2007/10/02)
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- Process for formation of base and light-sensitive material
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A process for formation of a base, which comprises reacting an acetylide compound with a salt. The acetylide compound has the following formula: wherein R is a monovalent group selected from the group consisting of an alkyl group, a cycloalkyl group, an alkenyl group, an alkynyl group, an aralkyl group, an aryl group and a heterocyclic group, each of which may have one or more substituent groups; M is an n-valent transition metal atom; and n is 1, 2 or 3. The salt is composed of an anion having an affinity for the transition metal (M) (the affinity of the anion for the transition metal is more than that of the acetylide anion (R--C C?)), and a cation derived from one selected from the group consisting of an alkali metal, an alkaline earth metal, ammonia and an organic base. A light-sensitive material containing the acetylide compound and the salt is also disclosed.
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- Syntheses and Reactivity of Acetylide-containing Clusters of Group 1B Metals. Stepwise Syntheses of Trinuclear - and Pentanuclear - and - Clusters
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The pentanuclear cluster - was obtained from the reaction between n> and a mixture of - and n>.Its structure is described.The same cluster has been synthesized in a stepwise manner starting with - through the binuclear complex - and the trinuclear cluster -.The synthesis of the analogous gold-silver cluster - was achieved by a slightly modified method.
- Abu-Salah, Omar M.,Al-Ohaly, Abdel Razzak A.
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p. 2297 - 2300
(2007/10/02)
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