618092-28-7Relevant articles and documents
Syntheses of highly unsaturated isocyanides via organometallic pathways
Mujkic, Monika,Lentz, Dieter
, p. 839 - 849 (2012)
The carbon carbon coupling reaction by nucleophilic attack of (CO) 5Cr(CN-CFCF2) 1 by lithium or Grignard compounds 2a-i yields the isocyanide complexes (CO)5Cr(CN-CFCF-R) 3a-i (a R = CHCH2, b R = CHCF2, c R = CCH, d R = CC-SiMe3, e R = CC-Ph, f R = CC-C6F4OMe, g R = CC-C 6H3(CF3)2, h R = C6F 5, i R = C6H3(CF3)2) as mixtures of E and Z isomers. The dinuclear complexes 5a-c are obtained from the reaction of 1 with the dilithio or dimagnesium compound 4a-c as the Z,Z-, E,Z- and E,E-isomers, respectively. (CO)5Cr(CN-CFCF-CC-CC-CFCF-NC)Cr(CO) 57 is obtained as a mixture of Z,Z-, Z,E- and E,E-isomers from (CO)5Cr(CN-CFCF-CC-H 3d by Eglington-Glaser coupling. (CO) 5Cr(CN-CFCF-CC-CFCF-NC)Cr(CO)56 and (CO) 5Cr(CN-CFCF-CC-CC-CFCF-NC)Cr(CO)57 react with octacarbonyldicobalt forming the cluster compounds Z,Z-[{η2- μ2-(CO)5Cr(CN-CFCF-CC-CFCF-NC)Cr(CO) 5}Co2(CO)6] Z,Z-8, E,Z-[{η2- μ2-(CO)5Cr(CN-CFCF-CC-CFCF-NC)Cr(CO) 5}Co2(CO)6] E,Z-8 and E,E-[{η2- μ2-(CO)5Cr(CN-CFCF-CC-CFCF-NC)Cr(CO) 5}Co2(CO)6] E,E-8 and Z,Z-[{η2- μ2-(CO)5Cr(CN-CFCF-CC-CC-CFCF-NC)Cr(CO) 5}{Co2(CO)6}2] Z,Z-9, E,Z-[{η2-μ2-(CO)5Cr(CN-CFCF-CC-CC-CFCF- NC)Cr(CO)5}{Co2(CO)6}2] E,Z-9 and E,E-[{η2-μ2-(CO)5Cr(CN-CFCF-CC-CC-CFCF- NC)Cr(CO)5}{Co2(CO)6}2] Z,Z-9, respectively. The crystal and molecular structures of E-3d, Z-3h, Z,Z-8, E,Z-8 and Z,Z-9 were elucidated by single-crystal X-ray crystallography.
Pluripotent Features of Doubly Thiophene-Fused Benzodiphospholes as Organic Functional Materials
Higashino, Tomohiro,Ishida, Keiichi,Sakurai, Tsuneaki,Seki, Shu,Konishi, Tatsuki,Kamada, Kenji,Imahori, Hiroshi,Imahori, Hiroshi
supporting information, p. 6425 - 6438 (2019/04/26)
Linear ladder-type π-conjugated molecules have attracted much interest because of their intriguing physicochemical properties. To modulate their electronic structures, an effective strategy is to incorporate main-group elements into ladder-type π-conjugated molecules. In line with this strategy, a variety of ladder-type π-conjugated molecules with main-group elements have been synthesized to explore their potential utility as organic functional materials. In this context, phosphole-based π-conjugated molecules are highly attractive, owing to their unique optical and electrochemical properties, which arise from the phosphorus atom. Herein, the synthesis and physicochemical properties of doubly thiophene-fused benzodiphospholes, as a new class of phosphole-based ladder-type π-conjugated molecule, are reported. Systematic investigations into the physicochemical properties of doubly thiophene-fused benzodiphospholes revealed their pluripotent features: intense near-infrared fluorescence, excellent two-photon absorption property, and remarkably high electron-transporting ability. This study demonstrates the potential utility of doubly thiophene-fused benzodiphospholes as organic functional materials for biological imaging, nonlinear optics, organic transistors, and organic photovoltaics.
Catalytic Activation of Trimethylsilylacetylenes: A One-Pot Route to Unsymmetrical Acetylenes and Heterocycles
Lasányi, Dániel,Mészáros, ádám,Novák, Zoltán,Tolnai, Gergely L.
, p. 8281 - 8291 (2018/06/11)
For the synthesis of unsymmetrical acetylenes, a Sonogashira coupling-deprotection-Sonogashira coupling reaction sequence is often used. Removal of protecting groups requires harsh conditions or an excess of difficult to handle and expensive reagents. Herein, we disclose a novel catalytic method for the selective deprotection of trimethylsilylacetylenes in Sonogashira reaction. The reagent hexafluorosilicic acid, an inexpensive nontoxic compound, was used to promote the selective desilylation. This method enables the efficient synthesis of unsymmetric acetylenes with other silylated functional groups present. Further possibilities of the method were explored by synthesis of heterocycles.
