C. Carfagna et al., NUCLEOPHILIC-ATTACK AT THE CENTRAL ALLYL CARBON-ATOM IN [(ETA-3-ALLYL)ML2]- EXPERIMENTAL FACTS AND NEW THEORETICAL INSIGHTS( COMPLEXES (M =PD, PT) ), Organometallics, 12(8), 1993, pp. 3019-3028
The reaction of ketene silyl acetals with [(eta3-allyl)PtL2]+OAc- lead
s to formation of platina-(II)cyclobutanes upon the nucleophilic attac
k of the enolate at the central allyl carbon atom (C(c)). As a result,
from a new theoretical analysis for complexes of the type [(eta3-ally
l)ML2]+ (M = Pd, Pt), the C(c)-centered MO (C3-pi(perpendicular-to))
is not destabilized as usually assumed. Rather, it competes with anoth
er MO, (d(pi)-nC3) (centered on metal and terminal C(t) carbon atoms),
to be the first LUMO of the system. On this basis, the attack of a nu
cleophile at the C(c) atom is almost as probable as attack at the C(t)
atoms. The initial MO picture of the precursor complex can only sugge
st the regioselectivity of the reaction, saying nothing about the attr
active/repulsive interactions encountered by the incoming nucleophile
in the pathway toward metallacyclobutane. Within the limits imposed by
the EHMO method, a simple qualitative description is offered of the i
ntended correlations among metal-carbon and carbon-nucleophile bonding
/antibonding MO's during the formation of the metallacyclobutane produ
ct. An energetic barrier, which varies as a function of the sigma-dono
r strength of the nucleophile, is observed, and its origin is describe
d.