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

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-iPr₂C₆H₃; cAAC^Me = C{(NDipp)CMe₂CH₂CMe₂}; cAAC^Cy = C{(NDipp)CMe₂CH₂C(Cy)}, Cy = cyclohexyl) containing a C[double bond, length as m-dash]C-P[double bond, length as m-dash]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<

SUBMITTER: Sharma MK 

PROVIDER: S-EPMC8148328 | biostudies-literature | 2020 Jan

REPOSITORIES: biostudies-literature