NDLI: Synthesis of Li/OR phosphinidenoid complexes: on the evidence for intramolecular O–Li donation and the effect of cation encapsulation

Content Provider	World Health Organization (WHO)-Global Index Medicus
Author	Duan, Lili Streubel, Rainer Kyri, Andreas Wolfgang Schnakenburg, Gregor
Description	Author Affiliation: Streubel R ( Institut für Anorganische Chemie, Rheinische Friedrich-Wilhelms-Universität Bonn, Gerhard-Domagk-Str. 1, 53121 Bonn, Germany. r.streubel@uni-bonn.de.)
Abstract	Synthesis of phosphinite complexes 12–14a–c, 15a and 16a was achieved via reaction of transient Li/Cl phosphinidenoid complexes 6–10, prepared from dichloro(organo)phosphane complexes $[(OC)_{5}M\{RPCl_{2}\}]$ 1–5 (1,6: R = $CPh_{3},$ 2,7: R = $C_{5}Me_{5},$ 3–5, 8–10: R = $CH(SiMe_{3})_{2},$ 1–3, 6–8: M = W, 9: M = Mo, 10: M = Cr), with different alcohols 11a–c (a: R = allyl, b: R = methyl, c: R = isopropyl). Deprotonation of complexes 12b, 13b with MeLi or $^{t}BuLi$ in the presence of two equivalents of 12-crown-4 led to the selective formation of phosphinidenoid complexes $[Li(12-crown-4)_{2}]$ $[(OC)_{5}W\{RP(OCH_{3})\}]$ (18a R = $CPh_{3}$ and 18b R = $C_{5}Me_{5})$ which were stable in solution at ambient temperature, in contrast to Li/OMe phosphinidenoid complexes without 12-crown-4. To our surprise attempts to crystallise complex 18b yielded complex 21 having a Li–O–P subunit. The reaction of complex 17c with $[Ph_{3}C]BF_{4}$ yielded the P–C coupling product 26 and, hence, the first evidence for an oxidative SET reaction. All isolated products were characterised by multinuclear NMR spectroscopy, IR, MS and single-crystal X-ray crystallography in the case of complexes 12a,b, 13b, 14a–c, 15a, 16a and 21.
ISSN	14779226
Issue Number	5
Journal	Dalton Trans.
Volume Number	43
e-ISSN	13645447
Language	English
Publisher	Royal Society of Chemistry
Publisher Date	2014-02-07
Publisher Place	Great Britain (UK)
Access Restriction	Subscribed
Subject Keyword	Chemistry
Content Type	Text
Resource Type	Article
Subject	Inorganic Chemistry

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