English
 
Help Privacy Policy Disclaimer
  Advanced SearchBrowse

Item

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

Sharma, M. K., Blomeyer, S., Glodde, T., Neumann, B., Stammler, H.-G., Hinz, A., 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. doi:10.1039/C9SC05598C.

Item is

Basic

show hide
Genre: Journal Article

Files

show Files

Locators

show

Creators

show
hide
 Creators:
Sharma, Mahendra K.1, Author
Blomeyer, Sebastian1, Author
Glodde, Timo1, Author
Neumann, Beate1, Author
Stammler, Hans-Georg1, Author
Hinz, Alexander2, Author
van Gastel, Maurice3, Author              
Ghadwal, Rajendra S.1, Author
Affiliations:
1Molecular Inorganic Chemistry and Catalysis, Inorganic and Structural Chemistry, Center for Molecular Materials, Faculty of Chemistry, Universität Bielefeld, Universitätsstrasse 25, Bielefeld, D-33615, Germany, ou_persistent22              
2Institute of Inorganic Chemistry, Karlsruhe Institute of Technology (KIT), Engesserstr. 15, D-76131 Karlsruhe, Germany, ou_persistent22              
3Research Group van Gastel, Max-Planck-Institut für Kohlenforschung, Max Planck Society, ou_2541713              

Content

show
hide
Free keywords: -
 Abstract: A synthetic strategy for the 2-phospha-1,3-butadiene derivatives [{(IPr)C(Ph)}P(cAACMe)] (3a) and [{(IPr)C(Ph)}P(cAACCy)] (3b) (IPr = C{(NDipp)CH}2, Dipp = 2,6-iPr2C6H3; cAACMe = C{(NDipp)CMe2CH2CMe2}; cAACCy = C{(NDipp)CMe2CH2C(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 GaCl3 to afford radical cations [{(IPr)C(Ph)}P(cAACR)]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 31P nucleus. Further one-electron removal from the radical cations 4a and 4b is also feasible with GaCl3, affording the dications [{(IPr)C(Ph)}P(cAACR)](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.

Details

show
hide
Language(s): eng - English
 Dates: 2019-11-052020-01-052020-01-062020-02-21
 Publication Status: Published in print
 Pages: 10
 Publishing info: -
 Table of Contents: -
 Rev. Type: Peer
 Identifiers: DOI: 10.1039/C9SC05598C
 Degree: -

Event

show

Legal Case

show

Project information

show

Source 1

show
hide
Title: Chemical Science
  Other : Chem. Sci.
Source Genre: Journal
 Creator(s):
Affiliations:
Publ. Info: Cambridge, UK : Royal Society of Chemistry
Pages: - Volume / Issue: 11 (7) Sequence Number: - Start / End Page: 1975 - 1984 Identifier: ISSN: 2041-6520
CoNE: https://pure.mpg.de/cone/journals/resource/2041-6520