ISSN:
0009-2940
Keywords:
Phosphaalkenes, C-halo, C-metal
;
“Phospha-isonitrile”
;
Phosphinylidenemethylene
;
Phosphaalkyne, E/Z isomers
;
Chemistry
;
Inorganic Chemistry
Source:
Wiley InterScience Backfile Collection 1832-2000
Topics:
Chemistry and Pharmacology
Notes:
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-iodophosphaalkenes Mes* P = Cl2 (1 C) and Mes*P = CHI (2c) undergo halogen-metal exchange with n-BuLi at low temperatures. The resulting carbenoids Mes*P = CILi (11 c) and Mes*P = CHLi (6) reacted with ClMMe3 (M = Si, Ge, Sn) to give Mes*P=CIMMe3 [(Z)-13: M = Ge; (Z)-14: M = Sn] or Mes*P = CHMMe3 (8-10), respectively. Further reaction of (Z)-13 and (Z)-14 with nBuLi and ClMMe3 gave Mes*P=C(MMe3 (18: M=Ge; 19: M = Sn). The carbenoid (Z)-11 c decomposed at -85°C; instead of the expected “phosphaisonitrile” Mes*P = C : (21), only Mes*C≡P (15) was obtained which lends experimental support to the theoretically predicted instability of 21.
Additional Material:
2 Tab.
Type of Medium:
Electronic Resource
URL:
http://dx.doi.org/10.1002/cber.19911241207
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