Synthesis, Crystal and Electronic Structures of a Thiophosphinoyl‐ and Amino‐Substituted Metallated Ylide. Issue 11 (27th September 2021)

• Record Type: Journal Article
• Authors: Jörges, Mike; Kroll, Alexander; Kelling, Leif; Gauld, Richard; Mallick, Bert; Huber, Stefan M.; Gessner, Viktoria H.
• Is Part Of: ChemistryOpen. Volume 10:Issue 11(2021)
• Page Start: 1089
• Page End: 1094
• Publication Date: 2021-09-27
• Subjects: alkali metals -- lithium -- potassium -- structure elucidation -- ylide ligands; Chemistry -- Periodicals; 540; 540.5
• DOI: 10.1002/open.202100187
• Languages: English
• ISSNs: 2191-1363

Abstract

Abstract: α‐Metallated ylides have revealed themselves to be versatile reagents for the introduction of ylide groups. Herein, we report the synthesis of the thiophosphinoyl and piperidyl (Pip) substituted α‐metallated ylide [Ph2 (Pip)P=C−P(S)Ph2 ]M (M=Li, Na, K) through a four‐step synthetic procedure starting from diphenylmethylphosphine sulfide. Metallation of the ylide intermediate was successfully accomplished with different alkali metal bases delivering the lithium, sodium and potassium salts, the latter isolable in high yields. Structure analyses of the lithium and potassium compounds in the solid state with and without crown ether revealed different aggregates (monomer, dimer and hexamer) with the metals coordinated by the thiophosphoryl moiety and ylidic carbon atom. Although the piperidyl group does not coordinate to the metal, it significantly contributes to the stability of the yldiide by charge delocalization through negative hyperconjugation. Abstract : The synthesis and structures of the thiophosphoryl‐ and amino‐substituted metallated ylide [Ph2 (Pip)P=C−P(S)Ph2 ]M (M=Li, Na, K) are reported. The structures of the alkali metal salts (hexamer, dimer, monomer) reflect the stabilizing effects responsible for charge delocalization and show that the piperidyl moiety, albeit not coordinating to the metal, decisively contributes to the overall stability of the yldiide.