Treatment of the rhodium pincer complexes [RhCl(RPm)] (RPm = ,'-bis(di-R-phosphinomethyl)perimidinylidene, R = Ph, Cy) with triphenylcyclopropenium hexafluorophosphate affords rhodacyclobutadiene complexes. These in turn react with activated alkynes (RCCCOMe, R = H, COMe) to afford unusually stable cyclopropenylvinyls, implicating the intermediacy of σ-cyclopropenyl isomers. In contrast, treatment of [RhCl{py(NHPBu)-2,6}] with the same reagent instead results in double functionalisation (Ar) at the pincer backbone.
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Stable cyclopropenylvinyl ligands insertion into a transient cyclopropenyl metal bond.
Dalton Trans
February 2024
Research School of Chemistry, Australian National University, Canberra, Australian Capital Territory, ACT 2601, Australia.
Treatment of the rhodium pincer complexes [RhCl(RPm)] (RPm = ,'-bis(di-R-phosphinomethyl)perimidinylidene, R = Ph, Cy) with triphenylcyclopropenium hexafluorophosphate affords rhodacyclobutadiene complexes. These in turn react with activated alkynes (RCCCOMe, R = H, COMe) to afford unusually stable cyclopropenylvinyls, implicating the intermediacy of σ-cyclopropenyl isomers. In contrast, treatment of [RhCl{py(NHPBu)-2,6}] with the same reagent instead results in double functionalisation (Ar) at the pincer backbone.
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