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Synthesis and Reactions of P ‐Supermesityl‐ C ‐halophosphaalkenes
Author(s) -
Goede Simon J.,
Bickelhaupt Friedrich
Publication year - 1991
Publication title -
chemische berichte
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.667
H-Index - 136
eISSN - 1099-0682
pISSN - 0009-2940
DOI - 10.1002/cber.19911241207
Subject(s) - chemistry , carbenoid , halogen , stereochemistry , medicinal chemistry , yield (engineering) , metal , reaction conditions , catalysis , alkyl , organic chemistry , rhodium , physics , thermodynamics
C‐Halophosphaalkenes ( 1, 2 ) were prepared in high yield by a one‐pot synthesis from HCX 3 or CI 4 and Mes* PCl 2 (Mes* supermesityl 2,4,6‐tri‐tert‐butylphenyl). The C‐iodophosphaalkenes Mes* P Cl 2 ( 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 ClMMe 3 (M Si, Ge, Sn) to give Mes*PCIMMe 3 [(Z)‐ 13 : M Ge; (Z)‐14: M Sn] or Mes*P CHMMe 3 ( 8 – 10 ), respectively. Further reaction of (Z)‐ 13 and (Z)‐ 14 with n BuLi and ClMMe 3 gave Mes*PC(MMe 3 ( 18 : MGe; 19 : M Sn). The carbenoid (Z)‐ 11 c decomposed at −85°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 .