Preparation of Complexes Bearing N-Alkylated, Anionic or Protic CAACs Through Oxidative Addition of 2-Halogenoindole Derivatives.

ABSTRACT: CAAC precursors 2-chloro-3,3-dimethylindole 1 and 2-chloro-1-ethyl-3,3-dimethylindolium tetrafluoroborate 2BF₄ have been prepared and oxidatively added to [M(PPh₃ )₄ ] (M=Pd, Pt). Salt 2BF₄ reacts with [Pd(PPh₃ )₄ ] in toluene at 25?°C over 4?days to yield complex cis-[3]BF₄ featuring an N-ethyl substituted CAAC, two cis-arranged phosphines and a chloro ligand. Compound trans-[3]BF₄ was obtained from the same reaction at 80?°C over 1?day. Salt 2BF₄ reacts with [Pt(PPh₃ )₄ ] to give cis-[4]BF₄ . The neutral indole derivative 1 adds oxidatively to [Pt(PPh₃ )₄ ] to give trans-[5] featuring a CAAC ligand with an unsubstituted ring-nitrogen atom. This nitrogen atom has been protonated with py?HBF₄ to give trans-[6]BF₄ bearing a protic CAAC ligand. The Pd^II complex trans-[7]BF₄ bearing a protic CAAC ligand was obtained in a one-pot reaction from 1 and [Pd(PPh₃ )₄ ] in the presence of py?HBF₄ .

SUBMITTER: Termuhlen S 

PROVIDER: S-EPMC7898591 | biostudies-literature | 2021 Feb

REPOSITORIES: biostudies-literature