Norbornadiene complexes with platinum

Norbornadiene complexes of platinum and palladium 14 reacted with silver carboxylates to form the carboxymetalation products 15 which, on treatment with triphenylphosphane, underwent intramolecular alkene insertion to form the nortricyclene skeleton 16. Reductive decom-plexation gave the acylated tricyclo[2.2.1.0 ]heptan-ex n-3-ol 17. ... 

In contrast to the behavior with platinum, a number of rhodium(I) and iridium(III) complexes react with cycloheptatriene to form complexes of the isomeric bicyclic chelate diolefin, norbornadiene (15,137). 

The ligand ap reacts with (norbornadiene) M (CO) 4 (M = Cr, Mo, W) (vide infra), to give complexes (phosphine) M (CO)4. The phosphine is not coordinated as ap but as ortho-cis-propenyl-phenyldiphenylphosphine (pp) the production of this species is discussed below. There is no evidence that this isomerisation takes place on coordination to platinum (II) or palladium(II). The chelate complex PtBr2 (pp) was prepared by Interrante (20) and shown by its spectral properties to be distinct from PtBr2 (ap). 

Platinum f-butyl peroxide trifluoroacetate, (CF CC PtlOOCCCh KCHaV COH j 2 (1). Mol. wt. 1168.72, orange powder. This peroxidic complex is prepared by the reaction of f-butyl hydroperoxide with (norbornadiene)Pt(CF3C02)2. 

Conversion of norbornadiene to nortricyclenes can also be achieved with organomercurials. This reaction proceeds via transmetalation to form a c-bonded organopalladium system which inserts norbornadiene. Thus an enrfo-cw-addition is observed. Conversions of this type were observed in the phenylation of dichloro(t -norbornadiene)palladium either with diphenyl-mercury or, more conveniently, with sodium tetraphenylborate to give di-/r-chlorobis(2 5,6-t -c ffo-3-phenylbicyclo[2.2.1]hept-e /o-2-yl)palladium (30) via cis addition.By contrast, the analogous platinum complex did not give a phenylation product. The palladium complex 30 underwent reversible ring closure to a nortricyclenyl complex 31 with pyridine. ... 

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