Lead enolato complexes

AcMes has been chosen as a model ketone for deprotonation since its enolato complexes have excellent crystallization properties with a variety of cations. Thus, the reaction of AcMes with KHMDS in PhMe gives the type 9 complex [K4 /Z3-OC(=CH2)Mes 4 (PhMe)4] (type 9 and with NaBu-n and tmeda leads to the sodium enolato complex [Na2 /z-OC(=CH2)Mes 2(tmeda)2] (type 8) . 

Equimolar amounts of EDA and 48 give the corresponding lithium enolato complex which, by means of a Claisen-type condensation, leads to 49, which, in turn, reacts with [Zr(r 5-Cp)2(Me)Cl] to give 50 1... 

Complex 23a (L = PMes) reacts with KOC(=CH2)Me to afford a 70 30 mixture of 24a and 25a which, npon thermolysis, leads to methane and a mixture of 26 and the prodnct of phosphine dissociation 27 . 23a and KOC(=CH2)CH2Bu-t also provide an eqnUibrinm mixtnre of enolato and 2-oxoalkyl complexes 24b and 25b, which has also been observed between complexes frawi-[Rh OC(=CHR")R (CO)(PR3)2] (R = R = Ph, R" = H and R = R" = Me, R = f-Bn) and their 2-oxoalkyl isomers. Complex 28, containing a dianionic enolato hgand, reacts with AcCH2Bn-f at 110°C to afford the S-diketonato complex 29 , which can also be obtained by reacting 23b with two eqnivalents of KOC(=CH2)CH2Bn-f3. ... 

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