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Light-induced rearrangement of thioether-substituted phosphanide ligands : Scope and limitations of a remarkable isomerization

Izod, Keith, Clark, Ewan R., Foster, Pamela, Percival, Rebecca J., Riddlestone, Ian M., Clegg, William, Harrington, Ross W. (2013) Light-induced rearrangement of thioether-substituted phosphanide ligands : Scope and limitations of a remarkable isomerization. Chemistry - A European Journal, 19 (19). pp. 6094-6107. ISSN 0947-6539. (doi:10.1002/chem.201203918) (The full text of this publication is not currently available from this repository. You may be able to access a copy if URLs are provided)

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Official URL
http://www.dx.doi.org/10.1002/chem.201203918

Abstract

Treatment of the thioether-substituted secondary phosphanes R 2PH(C6H4-2-SR1) [R 2=(Me3Si)2CH, R1=Me (1 PH), iPr (2PH), Ph (3PH); R2=tBu, R1=Me (4PH); R2=Ph, R1=Me (5 PH)] with nBuLi yields the corresponding lithium phosphanides, which were isolated as their THF (1-5Pa) and tmeda (1-5Pb) adducts. Solid-state structures were obtained for the adducts [R 2P(C6H4-2-SR1)]Li(L)n [R2=(Me3Si)2CH, R1=nPr, (L) n=tmeda (2Pb); R2=(Me3Si) 2CH, R1=Ph, (L)n=tmeda (3Pb); R 2=Ph, R1=Me, (L)n=(THF)1.33 (5 Pa); R2=Ph, R1=Me, (L)n=([12]crown- 4)2 (5Pc)]. Treatment of 1PH with either PhCH2Na or PhCH2K yields the heavier alkali metal complexes [{(Me3Si)2CH}P(C6H 4-2-SMe)]M(THF)n [M=Na (1Pd), K (1 Pe)]. With the exception of 2Pa and 2Pb, photolysis of these complexes with white light proceeds rapidly to give the thiolate species [R2P(R1)(C6H 4-2-S)]M(L)n [M=Li, L=THF (1Sa, 3 Sa-5Sa); M=Li, L=tmeda (1Sb, 3 Sb-5Sb); M=Na, L=THF (1Sd); M=K, L=THF (1 Se)] as the sole products. The compounds 3Sa and 4 Sa may be desolvated to give the cyclic oligomers [[{(Me 3Si)2CH}P(Ph)(C6H4-2-S)]Li] 6 ((3S)6) and [[tBuP(Me)(C6H 4-2-S)]Li]8 ((4S)8), respectively. A mechanistic study reveals that the phosphanide-thiolate rearrangement proceeds by intramolecular nucleophilic attack of the phosphanide center at the carbon atom of the substituent at sulfur. For 2Pa/2Pb, competing intramolecular β-deprotonation of the n-propyl substituent results in the elimination of propene and the formation of the phosphanide-thiolate dianion [{(Me3Si)2CH}P(C6H4-2-S)] 2-. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Item Type: Article
DOI/Identification number: 10.1002/chem.201203918
Uncontrolled keywords: alkali metals, P ligands, photolysis, rearrangement, sulfur, Cyclic oligomers, Intramolecular nucleophilic attack, Light-induced, Mechanistic studies, P ligands, rearrangement, Solid-state structures, Thiolate species, Alkali metals, Ligands, Lithium, Metal complexes, Oligomers, Photolysis, Propylene, Sodium, Sulfur, Silicon
Subjects: Q Science > QD Chemistry
Divisions: Faculties > Sciences > School of Physical Sciences > Functional Materials Group
Depositing User: Giles Tarver
Date Deposited: 29 Jul 2015 15:11 UTC
Last Modified: 29 May 2019 14:56 UTC
Resource URI: https://kar.kent.ac.uk/id/eprint/49874 (The current URI for this page, for reference purposes)
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