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Isolation of singlet carbene derived 2-phospha-1,3-butadienes and their sequential one-electron oxidation to radical cations and dications

Sharma, Mahendra K.; Blomeyer, Sebastian; Glodde, Timo; Neumann, Beate; Stammler, Hans-Georg; Hinz, Alexander; van Gastel, Maurice; Ghadwal, Rajendra S.

Abstract:
A synthetic strategy for the 2-phospha-1,3-butadiene derivatives [{(IPr)C(Ph)}P(cAAC$^{Me}$)] (3a) and [{(IPr)C(Ph)}P(cAAC$^{Cy}$)] (3b) (IPr = C{(NDipp)CH}$_{2}$, Dipp = 2,6-iPr$_{2}$C$_{6}$H$_{3}$; cAAC$^{Me}$ = C{(NDipp)CMe$_{2}$CH$_{2}$CMe$_{2}$}; cAAC$^{Cy}$ = C{(NDipp)CMe$_{2}$CH$_{2}$C(Cy)}, Cy = cyclohexyl) containing a C=C–P=C framework has been established. Compounds 3a and 3b have a remarkably small HOMO–LUMO energy gap (3a: 5.09; 3b: 5.05 eV) with a very high-lying HOMO (-4.95 eV for each). Consequently, 3a and 3b readily undergo one-electron oxidation with the mild oxidizing agent GaCl$_{3}$ to afford radical cations [{(IPr)C(Ph)}P(cAAC$^{R}$)]GaCl$_{4}$ (R = Me 4a, Cy 4b) as crystalline solids. The main UV-vis absorption band for 4a and 4b is red-shifted with respect to that of 3a and 3b, which is associated with the SOMO related transitions. The EPR spectra of compounds 4a and 4b each exhibit a doublet due to coupling of the unpaired electron with the $^{31}$P nucleus. Further oneelectron removal from the radical cations 4a and 4b is also feasible with GaCl$_{3}$, affording the dications [{(IPr)C(Ph)}P(cAAC$^{R}$)](GaCl$_{4}$)$_{2}$ (R = Me 5a, Cy 5b) as yellow crystals. ... mehr

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Verlagsausgabe §
DOI: 10.5445/IR/1000117849
Veröffentlicht am 24.03.2020
Originalveröffentlichung
DOI: 10.1039/c9sc05598c
Scopus
Zitationen: 4
Web of Science
Zitationen: 4
Cover der Publikation
Zugehörige Institution(en) am KIT Institut für Anorganische Chemie (AOC)
Publikationstyp Zeitschriftenaufsatz
Publikationsdatum 21.02.2020
Sprache Englisch
Identifikator ISSN: 2041-6520, 2041-6539
KITopen-ID: 1000117849
Erschienen in Chemical science
Verlag Royal Society of Chemistry (RSC)
Band 11
Heft 7
Seiten 1975–1984
Vorab online veröffentlicht am 06.01.2020
Nachgewiesen in Scopus
Web of Science
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