Simple access to ionic liquids and organic salts containing the phosphaethynolate (PCO⁻) and Zintl (Sb₁₁³⁻) anions

Abstract

Herein we report the synthesis of the first ionic liquids with the highly reactive and synthetically valuable phosphaethynolate (PCO(-)) anion. They are simply synthesised by the reaction of organic methylcarbonate salts with P(SiMe3)3. The products are obtained in near to quantitative yields and they are highly viscous liquids at room temperature or have low melting points for symmetric cations. Moreover, extending this synthetic strategy towards Sb(SiMe3)3 we discovered a simple synthesis for [P(nBu)3Me](+)3[Sb11](3-), the first organic cation salt comprising the Zintl-anion [Sb11](3-).

The Chemistry of the 2‐Phosphaethynolate Anion

“…[8] This method gives rise to avariety of salts,many of which behave as ionic liquids,and is highly tuneable,a llowing for the synthesis of an umber of ammonium and phosphonium salts of the 2-phosphaethynolate anion (at least three of which have been structurally authenticated). [8] This method gives rise to avariety of salts,many of which behave as ionic liquids,and is highly tuneable,a llowing for the synthesis of an umber of ammonium and phosphonium salts of the 2-phosphaethynolate anion (at least three of which have been structurally authenticated).…”

Salen supported Al–O–CP and Ga–PCO complexes

“…25 These results imply acid-base reactions to have occurred, in which presumably the salen ligands in 2a and 3 are deprotonated by the NHC and subsequently [OCP] − is liberated to form the [NHC-H] [OCP] ion pair. Note that 4 is a rare example of a phosphaethynolate anion with a weakly coordinating cation, 15,29 a related example of which could be accessed from the reaction of Na [OCP] with the non-methylated 1,3-diisopropyl imidazolium chloride (δ 31 P = −388.0 ppm; see the ESI † for synthetic details).…”

Cyanidosilikate – Synthese und Struktur

“…70 % Route A) führte. Zum anderen wurden Ammoniummethylcarbonate, ionische Flüssigkeiten mit einem zersetzbaren Anion, mit wässriger H 2 SiF 6 umgesetzt, wodurch tetraalkylierte Ammoniumsalze [R 3 NMe] 2 [SiF 6 ] (R=Ethyl, n ‐Propyl und n ‐Butyl) in sehr guten Ausbeuten (90 %) hergestellt werden konnten. Wir möchten darauf hinweisen, dass wir (gemäß 19 F‐NMR‐Experimenten) immer sehr dynamische Mischungen von [SiF 6 ] 2− , [SiF 5 ] − und F − in Lösung beobachtet haben (Abbildung S30), unabhängig davon, ob Syntheseweg A oder B gewählt wurde.…”