The synthesis and reactivity of rhodium pincer complexes featuring bulky, neutral POP ligands has been investigated. The new furan-based pincer ligand furPOP was developed for this study, and known bulky analogs of Xantphos were also employed. In general, these (POP)Rh species are more reactive in oxidative addition than their (PCP)Rh and (PNP)Rh isosteres, reflecting the importance of the trans influence of the ligand. Both (POP)RhCl and (POP)Rh(C2H4)+ react with H2 under mild conditions to afford classical dihydridochloride and dihydride complexes. The neutral monohydride (POP)RhH has been obtained and characterized crystallographically. Ethylene undergoes reversible insertion into the Rh-H bond of (POP)RhH, allowing a direct thermodynamic measurement of this catalytically relevant step. In some cases, the cationic and neutral (POP)Rh hydrides are entirely selective for insertion of ethylene over propylene. Further catalytic applications will be discussed.

Basic chemistry of POP pincer rhodium complexes: Unusual reactivity and selectivity in oxidative addition and migratory insertion reactions

244th National Meeting (2012)

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