136409-23-9Relevant academic research and scientific papers
Synthesis and Reactions of P-Supermesityl-C-halophosphaalkenes
Goede, Simon J.,Bickelhaupt, Friedrich
, p. 2677 - 2684 (2007/10/02)
C-Halophosphaalkenes (1, 2) were prepared in high yield by a one-pot synthesis from HCX3 or CI4 and Mes*PCl2 (Mes* = supermesityl = 2,4,6-tri-tert-butylphenyl).The C-iodophosphoaalkenes Mes*P=Cl2 (1c) and Mes*P=CHI (2c) undergo halogen-metal exchange with n-BuLi at low temperatures.The resulting carbenoids Mes*P=CILi (11c) and Mes*P=CHLi (6) reacted with ClMMe3 (M = Si, Ge, Sn) to give Mes*P=CIMMe3 or Mes*P=CHMMe3 (8-10), respectively.Further reaction of (Z)-13 and (Z)-14 with n-BuLi and ClMMe3 gave Mes*P=C(MMe3)2 (18: M = Ge; 19: M = Sn).The carbenoid (Z)-11c decomposed at -85 deg C; instead of the expected "phosphaisonitrile" Mes*P=C: (21), only Mes*CP (15) was obtained which lends experimental support to the theoretically predicted instability of 21.Key Words: Phosphaalkenes, C-halo, C-metal / "Phospha-isonitrile" / Phosphinylidenemethylene / Phosphaalkyne, E/Z isomers
