Pyrazolylborate−Zinc Alkoxide Complexes. 1. Basic Properties, Methylations, and Heterocumulene Insertions

While a solution of TpPh,MeZn−OH in methanol contains only traces of TpPh,MeZn−OMe, according to the equilibrium
constant K = 5.8 × 10-4, the reactions of TpPh,MeZn−OH with the electronegative alcohols trifluoroethanol and
hexafluoro-2-propanol easily yield TpPh,MeZn−OCH2CF3 and TpPh,MeZn−OCH(CF3)2. The extremely hydrolytically
sensitive TpPh,MeZn−OR complexes, with R = Me, Et, i-Pr, and CH2CH2F, as well as TpCum,MeZn−OR, with R = Me
and i-Pr, are accessible from the Tp*Zn−hydride complexes and the corresponding alcohol. Alkylations with methyl
iodide have revealed the high nucleophilicity of TpPh,MeZn−OMe by conversion to dimethyl ether and TpPh,MeZn−I.
This conversion occurs rapidly not only with pure TpPh,MeZn−OMe but also with TpPh,MeZn−OH (as such or in the
presence of methanol) and with TpPh,MeZn−OCOOMe. A relation of the Tp*Zn−alkoxides to the function of the zinc
enzyme alcoholdehydrogenase exists in the reaction of TpPh,MeZn−OCH(CH3)2 with aromatic aldehydes, which yields
acetone and the corresponding benzyl oxides TpPh,MeZn−OH2Ar. The heterocumulenes carbon dioxide, carbon
disulfide, isothiocyanates, and one isocyanate are inserted into the Zn−OR bonds, yielding one alkyl carbonate
complex (TpPh,MeZn−OC(O)OMe), two xanthogenate complexes (TpPh,MeZn−SC(S)OR), three iminothiocarbonate
complexes (TpPh,MeZn−SC(NR‘)OR), and one alkyl carbamate complex (TpPh,MeZn−NR−COOMe). All insertion
reactions can be described by a common mechanism involving a four-center intermediate in which the most basic
heteroatom of the heterocumulene is attached to zinc.