Organoplatinum chemistry
Organoplatinum chemistry is the chemistry of organometallic compounds containing a carbon to platinum chemical bond, and the study of platinum as a catalyst in organic reactions. Organoplatinum compounds exist in oxidation state 0 to IV, with oxidation state II most abundant. The general order in bond strength is Pt-C (sp) > Pt-O > Pt-N > Pt-C (sp3). Organoplatinum and organopalladium chemistry are similar, but organoplatinum compounds are more stable and therefore less useful as catalysts.
Most organoplatinum(0) compounds contain alkene and alkyne ligands. Carbonyl complexes are rare, and the analogue of Ni(CO)4 is elusive. The alkene and alkyne ligands serve as two-electron donors, for example in the complexes (PPh3)2Pt(C2H4) and (PPh3)2Pt(C2Ph2). The ethylene ligand in (PPh3)2Pt(C2H4) is labile and exchanges with alkynes and electrophilic alkenes, even C60 a fullerene.
A general synthetic route to (PPh3)2Pt(un) (un = alkene, alkyne) is reduction of potassium tetrachloroplatinate with ethanolic potassium hydroxide or hydrazine in presence of a phosphine ligand such as triphenylphosphine and the alkene or alkyne. Such reactions proceed via the intermediacy of cis-dichlorobis(triphenylphosphine)platinum(II). Nitrogen-based ligands do not often support the formation of platinum complexes of alkenes and alkynes.
Zerovalent organoplatinum complexes lacking phosphine ligands are often prepared via PtCl2(COD).
where C7H10 is norbornene.
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