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Protonated diolefin complexes: Model systems for C;h activation via metal complexation
Author(s) -
Piantini Umberto,
Philipsborn Wolfgang Von,
Salzer Albrecht,
Buchmann Brigitte
Publication year - 1987
Publication title -
helvetica chimica acta
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.74
H-Index - 82
eISSN - 1522-2675
pISSN - 0018-019X
DOI - 10.1002/hlca.19870700606
Subject(s) - agostic interaction , chemistry , protonation , deprotonation , cationic polymerization , hydride , pyridine , nmr spectra database , stereochemistry , crystallography , medicinal chemistry , proton nmr , metal , spectral line , polymer chemistry , organic chemistry , physics , astronomy , ion
On protonation of the diolefin complexes [M(C 5 R 5 )(diene)] (R = H, CH 3 ; M = Co, Rh, Ir; diene = 2,3‐dimethylbutadiene, 1,3‐cyclohexadiene) with HBF 4 , cationic species are isolated which, at room temperature, show fluxional behaviour on the NMR time scale. Depending on R and M, three different ground states are observed for these cationic complexes in the NMR spectra at low temperatures. While for M = Ir a classical metal‐hydride structure M–H is observed, the Co and Rh complexes show ground states with ‘agostic’ H‐bridges M‥H‥C. The protonated species are characterized by 1 H‐, 13 C‐ and 103 Rh‐NMR spectra. Total line‐shape analysis of the 1 H and 13 C spectra in the 298–154 K range gave the free enthalpies of activation Δ G ≠ for methyl rotation and 1, 4‐H shift in the agostic structures 2b , 2b′ , 2c , and 2c′ . The Rh complexes show the lowest Δ G ± values for the 1,4‐H shift, and the strength of the agostic bond appears to decrease in the order CoC 5 H 5 > CoC 5 Me 5 > RhC 5 H 5 > RhC 5 Me 5 . Only for R = H and M = Rh and in the presence of traces of Lewis bases (H 2 O, Pyridine, or acetone), variable amounts of coordinatively saturated allyl complexes competing with the agostic species are observable. Morethan equimolar amounts of basic solvents lead to irreversible deprotonation and recovery of the starting complexes. Stable allyl‐halide complexes are formed on reaction with HCI, while protonation with HBF 4 , in the presence of CO, gives high yields of complexes [M(CO)(allyl)(C 5 R 5 )] [BF 4 ]. The different ground states observed for the protonated complexes and the dynamic behaviour in solution are compared with other hydride‐transfer reactions observed in organometallic chemistry, specifically with the β‐hydride elimination and the catalytic hydrogenation of olefins.