Abstract
The photolysis of [L 2Pt(C 2H 4)] (L = PPh 3, P( p-C 6H 4CH 3) 3 complexes in halocarbon solvents (CH 2Cl 2, CH 2Br 2) gives C 2H 4 and the coordinatively unsaturated species [L 2Pt]. Photolysis of platinum metallacycles [L 2Pt(CH 2) 4] (L = PPh 3, P(n-Bu) 3) generates alkanes, alkenes and [L 2Pt]. The [L 2Pt] centers are very reactive, and under prolonged photolysis undergo oxidative addition of CH 2Cl 2 forming the trans-[L 2Pt(CH 2Cl)Cl] complexes. Under appropriately controlled conditions the trans complexes isomerize to cis species before bimolecular C 2H 4 elimination occurs and [L 2PtCl 2] is formed as the final product. The oxidative addition-reductive elimination mechanism is discussed on the basis of spin-trapping experiments, quantum yield values, and the sensitivity to radical inhibitors and to solvents.
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