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Cyclic (amino)(aryl)carbenes (cAArCs) based on the isoindoline core were successfully generated in situ by α‐elimination of 3‐alkoxyisoindolines at high temperatures or by deprotonation of isoindol‐2‐ium chlorides with sodium or copper(I) acetates at low temperatures. 3‐Alkoxy‐isoindolines 2 a,b‐OR (R=Me, Et, iPr) have been prepared in high yields by the addition of a solution of 2‐aryl‐1,1‐diphenylisoindol‐2‐ium triflate (1 a,b‐OTf; a: aryl=Dipp=2,6‐diisopropylphenyl; b: Mesityl‐, Mes=2,4,6‐trimethylphenyl) to the corresponding alcohol (ROH) with NEt3 at room temperature. Furthermore, the reaction of 2 a,b‐OMe in diethyl ether with a tenfold excess of hydrochloric acid led to the isolation of the isoindol‐2‐ium chlorides 1 a,b‐Cl in high yields. The thermally generated cAArC reacts with sulfur to form the thioamide 3 a. Without any additional trapping reagent, in situ generation of 1,1‐diphenylisoidolin‐3‐ylidenes does not lead to the isolation of these compounds, but to the reaction products of the insertion of the carbene carbon atom into an ortho C−H bond of a phenyl substituent, followed by ring‐expansion reaction; namely, anthracene derivatives 9‐N(H)aryl‐10‐Ph‐C14H8 4 a,b (a: Dipp; b: Mes). These compounds are conveniently synthesized by deprotonation of the isoindol‐2‐ium chlorides with sodium acetate in high yields. Deprotonation of 1 a‐Cl with copper(I) acetate at low temperatures afforded a mixture of 4 a and the corresponding cAArC copper(I) chloride 5 a, and allowed the isolation and structural characterization of the first example of a cAArC copper complex of general formula [(cAArC)CuCl].
C\(_{19}\)H\(_{16}\)N\(_2\)OS, triclinic, P (1) over bar (no. 2), a= 8.1510(3) angstrom, b = 8.8021(3) angstrom, c =11.3953(5) angstrom, alpha =72.546(2)degrees, beta=84.568(2)degrees, gamma =80.760(2)degrees, V =768.86(5) angstrom(3), Z =2, R\(_{gt}\)(F) = 0.0491, WR\(_{ref}\)(F-2) = 0.1494, T =100 K.
Cyclic (amino)(aryl)carbenes (cAArCs) based on the isoindoline core were successfully generated in situ by α‐elimination of 3‐alkoxyisoindolines at high temperatures or by deprotonation of isoindol‐2‐ium chlorides with sodium or copper(I) acetates at low temperatures. 3‐Alkoxy‐isoindolines 2 a ,b‐OR (R=Me, Et, i Pr) have been prepared in high yields by the addition of a solution of 2‐aryl‐1,1‐diphenylisoindol‐2‐ium triflate (1 a ,b‐OTf ; a : aryl=Dipp=2,6‐diisopropylphenyl; b : Mesityl‐, Mes=2,4,6‐trimethylphenyl) to the corresponding alcohol (ROH) with NEt3 at room temperature. Furthermore, the reaction of 2 a ,b‐OMe in diethyl ether with a tenfold excess of hydrochloric acid led to the isolation of the isoindol‐2‐ium chlorides 1 a ,b‐Cl in high yields. The thermally generated cAArC reacts with sulfur to form the thioamide 3 a . Without any additional trapping reagent, in situ generation of 1,1‐diphenylisoidolin‐3‐ylidenes does not lead to the isolation of these compounds, but to the reaction products of the insertion of the carbene carbon atom into an ortho C−H bond of a phenyl substituent, followed by ring‐expansion reaction; namely, anthracene derivatives 9‐N(H)aryl‐10‐Ph‐C14H8 4 a ,b (a : Dipp; b : Mes). These compounds are conveniently synthesized by deprotonation of the isoindol‐2‐ium chlorides with sodium acetate in high yields. Deprotonation of 1 a‐Cl with copper(I) acetate at low temperatures afforded a mixture of 4 a and the corresponding cAArC copper(I) chloride 5 a , and allowed the isolation and structural characterization of the first example of a cAArC copper complex of general formula [(cAArC)CuCl].
The bis(N-heterocyclic carbene)(diphenylacetylene)palladium complex Pd(ITMe)\(_2\)(PhCCPh)] (ITMe=1,3,4,5-tetramethylimidazol-2-ylidene) acts as a highly active pre-catalyst in the diboration and silaboration of azobenzenes to synthesize a series of novel functionalized hydrazines. The reactions proceed using commercially available diboranes and silaboranes under mild reaction conditions.
Im Rahmen dieser Arbeit ist es gelungen, neue Boryl- und Borylenkomplexe von Palladium und Platin darzustellen. Die vollständige Charakterisierung dieser Verbindungen ermöglicht ees, Rückschlüsse auf die Natur der Metall-Bor-Bindung zu ziehen und trägt so zu einem besseren Verständnis dieser Substanzklasse bei. Überdies konnten bisher unbekoannte Koordinationsmodi für den Borliganden nachgewiesen werden. ...
Durch Umsetzung von monoanionischen Carbonylaten mit Bortrihalogeniden lassen sich Dihalogenborylkomplexe und verbrückte Halogenborylenkomplexe darstellen. Aus diesen Verbindungen lassen sich unter anderem basenstabilisierte Borylkomplexe, heterodinukleare Borylenkomplexe, metallbasenstabilisierte Metalloborylenkomplexe und kationische Borylenkomplexe darstellen.