Competition between vinylidene rearrangement and 1,2-insertion of carbon-disubstituted internal alkynes at a Cp*Ir(III) complex.
Competition between vinylidene rearrangement/1,1-insertion and 1,2-alkyne insertion into the Ir-Ar bond of [Cp*Ir(ppy-F4)](+) was observed on reaction with diarylacetylenes. The former process afforded the iridacycle 2via the subsequent 1,4-Ir migration, whereas the latter led to the pyridoisoquinolinium complex 4. Detailed analysis revealed that 4 isomerizes to 2 by heating at 50 °C.
Department of Applied Chemistry, Faculty of Science and Engineering, Chuo University, 1-13-27 Kasuga, Bunkyo-ku, Tokyo, Japan. yo-ishii@kc.chuo-u.ac.jp.
Yousuke
Y
Ikeda
Shintaro
S
Kodama
Noriko
N
Tsuchida
Youichi
Y
Ishii
D000114:Acetylene / Q000737:chemistry; D000480:Alkynes / Q000737:chemistry*; D002244:Carbon / Q000737:chemistry*; D005030:Ethylenes / Q000737:chemistry*; D007495:Iridium / Q000737:chemistry*; D009942:Organometallic Compounds / Q000737:chemistry*
D000480:Alkynes; D005030:Ethylenes; D009942:Organometallic Compounds; D007495:Iridium; D002244:Carbon; C036216:ethylene; D000114:Acetylene