Synthesis, Crystal and Electronic Structures of a Thiophosphinoyl‐ and Amino‐Substituted Metallated Ylide

ChemistryOpen

Mike Jörges¹  Prof. Dr. Viktoria H. Gessner¹  Dr. Richard Gauld¹  Prof. Dr. Stefan M. Huber¹  Dr. Alexander Kroll¹  Dr. Bert Mallick¹  Leif Kelling¹ 

[1] Faculty of Chemistry and Biochemistry Ruhr-University Bochum Universitätsstraße 150 44801 Bochum Germany;

关键词: alkali metals;    lithium;    potassium;    structure elucidation;    ylide ligands;   

DOI  :  10.1002/open.202100187

来源: DOAJ

【 摘 要 】

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.

【 授权许可】

Unknown