From a Stable Dianion to a Stable Carbenoid

Abstract

Robust und reaktionsfähig: Das erste bei Raumtemperatur stabile Li/Cl‐Carbenoid wurde durch die Oxidation eines geminalen Dianions unter milden Bedingungen erzeugt (siehe Schema). DFT‐Rechnungen erklären die elektronischen Ursachen dieser ungewöhnlichen Stabilität. Die Reaktivität des Carbenoids wurde am Beispiel der Bildung eines Palladiumcarbenkomplexes untersucht.

A Tin Analogue of Carbenoid: Isolation and Reactivity of a Lithium Bis(imidazolin‐2‐imino)stannylenoid

“…Ther eaction of 1 with Me 3 SiCl furnishes at in(II) dimer (4), which features ac hloro-functionalized N 2 Sn 2 ring. Compound 1 reacts with I 2 or MeI to afford the diiodostannane 2 or iodomethylstannane 3,r espectively,w ith concomitant elimination of LiCl.…”

“…[3d] In 2007, Le Floch and co-workers isolated the first room-temperature-stable carbenoid ( Figure 1, III)bychlorination of the corresponding dianion. [4] Remarkably, III is stable up to 60 8 8Ca saresult of coordination of the lithium cation by the thiophosphinoyl ligands tethered to the carbenoid center and two molecules of diethylether,w hich prevents the elimination of lithium chloride.S ince then, several isolable carbenoids have been reported by implementing asimilar stabilization method. [5] In sharp contrast, heavier analogues of carbenoids,that is metallylenoids of type R 2 EMX (E = Si, Ge,S n, Pb), have been only marginally studied.…”

Synthesis and Redox Behaviour of the Chalcogenocarbonyl Dianions [(E)C(PPh2S)2]2−: Formation and Structures of Chalcogen–Chalcogen Bonded Dimers and a Novel Selone

“…In contrast with the formation of chalcogen-chalcogen bonds upon oxidation of Nbridged ligands of type 1, [11] treatment of Li 2 2 with the mild oxidising agents C 2 Cl 6 or I 2 produces remarkably stable monomeric or dimeric carbenoids, respectively. [12,13] The nu- Keywords: chalcogens · electronic structure · oxidation · radicals · tridentate ligands…”

Alkali Metal Carbenoids: A Case of Higher Stability of the Heavier Congeners

“…[9,27] However,t his method has often been limited by side-reactions associated with the high reactivity and low stability of carbenoids. Ar 2 PPAr 2 ,with Ar = p-MeC 6 H 4 ), thus confirming their ambiphilic nature and their ability to eliminate MCl (see the Supporting Information for details).…”

“…Thef irst isolation of al ithium/halogen (Li/Hal) carbenoid was reported in 1993 by Boche et al (Figure 1). [9] Such stabilized carbenoids finally led to the revelation of novel reactivity patterns,s uch as an application in bond activation and coupling reactions. [9] Such stabilized carbenoids finally led to the revelation of novel reactivity patterns,s uch as an application in bond activation and coupling reactions.…”