Organometallic
projects currently underway in our laboratory involve bond activation
with platinum and palladium, tungsten carbene and carbyne chemistry,
and stereoselective addition reactions of coordinated ligands.
Three specific projects are summarized below.
The
utility of transition metal carbene reagents has blossomed dramatically
during the past decade. Electron-rich carbene complexes, [Tp'(OC)2W=CHR]- anions
have been prepared, and these complexes exhibit unusual reactivity
patterns at the carbene carbon. The availability of a heteroatom
carbene complex, Tp'I(O)W=C(CH3)(OSiR3),
in the Schrock manifold of oxidation states provides an opportunity
to define the reactivity patterns available to this class of carbene
complexes.
We
have developed robust Pt(IV) organometallic complexes containing
alkyl, hydride, aryl, acyl, formyl and silyl ligands in various
combinations with Tp' anchoring the octahedral coordination sphere.
The relevance of Pt(II)/Pt(IV) interconversions to alkane activation
processes provide the driving force for these synthetic efforts.
The
chiral [Tp'W(CO)(PhCºCR)]+ fragment
binds ketones and imines. These coordinated ketones or imines readily
add nucleophiles at carbon, and we are exploring the stereochemistry
of the reduced products.
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