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

Sharma MK, Blomeyer S, Glodde T, Neumann B, Stammler H-G, Hinz A, van Gastel M, Ghadwal R (2020)
CHEMICAL SCIENCE 11(7): 1975-1984.

Zeitschriftenaufsatz | Veröffentlicht | Englisch
 
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Abstract / Bemerkung
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)CMe2CH2CMe2}; cAAC(Cy) = C{(NDipp)CMe2CH2C(Cy)}, Cy = cyclohexyl) containing a Cxe001;C-Pxe001;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 GaCl3 to afford radical cations [{(IPr)C(Ph)}P(cAAC(R))]GaCl4 (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 P-31 nucleus. Further one-electron removal from the radical cations 4a and 4b is also feasible with GaCl3, affording the dications [{(IPr)C(Ph)}P(cAAC(R))](GaCl4)(2) (R = Me 5a, Cy 5b) as yellow crystals. The molecular structures of compounds 3-5 have been determined by X-ray diffraction and analyzed by DFT calculations.
Erscheinungsjahr
2020
Zeitschriftentitel
CHEMICAL SCIENCE
Band
11
Ausgabe
7
Seite(n)
1975-1984
ISSN
2041-6520
eISSN
2041-6539
Page URI
https://pub.uni-bielefeld.de/record/2941881

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Sharma MK, Blomeyer S, Glodde T, et al. Isolation of singlet carbene derived 2-phospha-1,3-butadienes and their sequential one-electron oxidation to radical cations and dications. CHEMICAL SCIENCE. 2020;11(7):1975-1984.
Sharma, M. K., Blomeyer, S., Glodde, T., Neumann, B., Stammler, H. - G., Hinz, A., van Gastel, M., et al. (2020). Isolation of singlet carbene derived 2-phospha-1,3-butadienes and their sequential one-electron oxidation to radical cations and dications. CHEMICAL SCIENCE, 11(7), 1975-1984. https://doi.org/10.1039/c9sc05598c
Sharma, M. K., Blomeyer, S., Glodde, T., Neumann, B., Stammler, H. - G., Hinz, A., van Gastel, M., and Ghadwal, R. (2020). Isolation of singlet carbene derived 2-phospha-1,3-butadienes and their sequential one-electron oxidation to radical cations and dications. CHEMICAL SCIENCE 11, 1975-1984.
Sharma, M.K., et al., 2020. Isolation of singlet carbene derived 2-phospha-1,3-butadienes and their sequential one-electron oxidation to radical cations and dications. CHEMICAL SCIENCE, 11(7), p 1975-1984.
M.K. Sharma, et al., “Isolation of singlet carbene derived 2-phospha-1,3-butadienes and their sequential one-electron oxidation to radical cations and dications”, CHEMICAL SCIENCE, vol. 11, 2020, pp. 1975-1984.
Sharma, M.K., Blomeyer, S., Glodde, T., Neumann, B., Stammler, H.-G., Hinz, A., van Gastel, M., Ghadwal, R.: Isolation of singlet carbene derived 2-phospha-1,3-butadienes and their sequential one-electron oxidation to radical cations and dications. CHEMICAL SCIENCE. 11, 1975-1984 (2020).
Sharma, Mahendra Kumar, Blomeyer, Sebastian, Glodde, Timo, Neumann, Beate, Stammler, Hans-Georg, Hinz, Alexander, van Gastel, Maurice, and Ghadwal, Rajendra. “Isolation of singlet carbene derived 2-phospha-1,3-butadienes and their sequential one-electron oxidation to radical cations and dications”. CHEMICAL SCIENCE 11.7 (2020): 1975-1984.
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