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

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...

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Autores principales:	Mike Jörges, Dr. Alexander Kroll, Leif Kelling, Dr. Richard Gauld, Dr. Bert Mallick, Prof. Dr. Stefan M. Huber, Prof. Dr. Viktoria H. Gessner
Formato:	article
Lenguaje:	EN
Publicado:	Wiley-VCH 2021
Materias:	alkali metals lithium potassium structure elucidation ylide ligands Chemistry QD1-999
Acceso en línea:	https://doaj.org/article/c77866bf6437453fa94bb2f917f861cd
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spelling	oai:doaj.org-article:c77866bf6437453fa94bb2f917f861cd2021-11-27T06:12:47ZSynthesis, Crystal and Electronic Structures of a Thiophosphinoyl‐ and Amino‐Substituted Metallated Ylide2191-136310.1002/open.202100187https://doaj.org/article/c77866bf6437453fa94bb2f917f861cd2021-11-01T00:00:00Zhttps://doi.org/10.1002/open.202100187https://doaj.org/toc/2191-1363Abstract 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.Mike JörgesDr. Alexander KrollLeif KellingDr. Richard GauldDr. Bert MallickProf. Dr. Stefan M. HuberProf. Dr. Viktoria H. GessnerWiley-VCHarticlealkali metalslithiumpotassiumstructure elucidationylide ligandsChemistryQD1-999ENChemistryOpen, Vol 10, Iss 11, Pp 1089-1094 (2021)
institution	DOAJ
collection	DOAJ
language	EN
topic	alkali metals lithium potassium structure elucidation ylide ligands Chemistry QD1-999
spellingShingle	alkali metals lithium potassium structure elucidation ylide ligands Chemistry QD1-999 Mike Jörges Dr. Alexander Kroll Leif Kelling Dr. Richard Gauld Dr. Bert Mallick Prof. Dr. Stefan M. Huber Prof. Dr. Viktoria H. Gessner Synthesis, Crystal and Electronic Structures of a Thiophosphinoyl‐ and Amino‐Substituted Metallated Ylide
description	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.
format	article
author	Mike Jörges Dr. Alexander Kroll Leif Kelling Dr. Richard Gauld Dr. Bert Mallick Prof. Dr. Stefan M. Huber Prof. Dr. Viktoria H. Gessner
author_facet	Mike Jörges Dr. Alexander Kroll Leif Kelling Dr. Richard Gauld Dr. Bert Mallick Prof. Dr. Stefan M. Huber Prof. Dr. Viktoria H. Gessner
author_sort	Mike Jörges
title	Synthesis, Crystal and Electronic Structures of a Thiophosphinoyl‐ and Amino‐Substituted Metallated Ylide
title_short	Synthesis, Crystal and Electronic Structures of a Thiophosphinoyl‐ and Amino‐Substituted Metallated Ylide
title_full	Synthesis, Crystal and Electronic Structures of a Thiophosphinoyl‐ and Amino‐Substituted Metallated Ylide
title_fullStr	Synthesis, Crystal and Electronic Structures of a Thiophosphinoyl‐ and Amino‐Substituted Metallated Ylide
title_full_unstemmed	Synthesis, Crystal and Electronic Structures of a Thiophosphinoyl‐ and Amino‐Substituted Metallated Ylide
title_sort	synthesis, crystal and electronic structures of a thiophosphinoyl‐ and amino‐substituted metallated ylide
publisher	Wiley-VCH
publishDate	2021
url	https://doaj.org/article/c77866bf6437453fa94bb2f917f861cd
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Synthesis, Crystal and Electronic Structures of a Thiophosphinoyl‐ and Amino‐Substituted Metallated Ylide

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