TITLE

Isocyanide insertion reactions into the Ta–C bonds of cationic and zwitterionic tantalocenes

AUTHOR(S)
Cook, Kevin S.; Piers, Warren E.; Patrick, Brian O.; McDonald, Robert
PUB. DATE
November 2003
SOURCE
Canadian Journal of Chemistry;Nov2003, Vol. 81 Issue 11, p1137
SOURCE TYPE
Academic Journal
DOC. TYPE
Article
ABSTRACT
The insertion of isonitriles R' NC (R' = t-Bu, C6H11, CH2C6H5) occurs exclusively into the Ta—CH2 bonds of the zwitterionic compounds (C5H4R)2Ta[CH2B(C6F5)3]CH3 (R = H, 1a; R = CH3, 1b) at relatively slow rates at room temperature to form N-out isomers as the sole kinetic products. By comparison, insertion of the same isonitrile substrates into a Ta—CH3 bond of the non-zwitterionic analogs [(C5H4R)2Ta(CH3)2][A] (R = H, A = B(C6F5)4, 3a; R = CH3, A = BF4, 3b) occurs much more rapidly, again to form N-out isomers exclusively under kinetic conditions. The difference in rate is attributed to the presence of a ground state α-agostic interaction in the zwitterionic compounds, which is not featured in the dimethyl ion pairs. All of the N-out isomers formed undergo thermal and irreversible conversion to the corresponding N-in isomers at rates that are conveniently followed by 1H NMR spectroscopy. The rates were studied at different temperatures to obtain activation parameters for each transformation. The rate and activation trends for this isomerization were analyzed as a function of the structural changes in the compounds. It was found that the rate decreased as the steric bulk of the isonitrile substitutent R' increased and that the rates were faster for the series that incorporated the more electron-donating C5H4CH3 ancillary ligand. Furthermore, isomerization rates for the zwitterionic N-out compounds were faster than those found in the non-zwitterionic series. This study represents one of the more extensive kinetic analyses of the rate of N-out to N-in isomerization as a function of structural changes. The observations are consistent with the mechanistic picture that has been developed for this process, involving dissociation of the η2 iminoacyl ligand, rotation about the M—Ciminoacyl bond and recoordination to the inside site of the metallocene wedge.
ACCESSION #
11548456

 

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