Reactions of low-valent metal complexes with fluorocarbons. Part 33. Bis(cyclo-octa-1,5-diene)platinum with hexafluorobut-2-yne; crystal and molecular structures of bis(cyclo-octa-1,5-diene)tetrakis(hexafluorobut-2-yne)triplatinum and bis(cyclo-octa-1,5-diene)bis(hexafluorobut-2-yne)diplatinum

Abstract

Reaction of [Pt(cod)₂](cod = 1,5-C₈H₁₂) with hexafluorobut-2-yne (hfb) affords [[graphic omitted](CF₃)}(cod)], which reacts with triphenylphosphine, carbon monoxide, or hexafluorobut-2-yne to afford [[graphic omitted](CF₃)}(PPh₃)₂], [[graphic omitted](CF₃)}(CO)₂(cod)], and [[graphic omitted](CF₃)}(cod)₂] containing three-, four-, six-, and eight-membered rings. The triplatinum species has been structurally identified by X-ray crystallography. The crystals are orthorhombic, space group Pbca, Z= 8 in a unit cell of dimensions a= 16.513(10), b= 28.536(30), and c= 15.429(8)Å. This complex Is also the major product in the reaction of [Pt(C₂H₄)₃] with hfb in the presence of cod. A minor product in this reaction, [[graphic omitted](CF₃)}(cod)₂], is formed in high yleld on treatment of [[graphic omitted](cod)₂] with hfb. A crystal-structure determination has established the presence in this molecule of a six-membered ring containing two platinum atoms. Crystals are triclinic, space group PZ= 2 in a unit cell of dimensions a= 11.099(5),b= 9,413(2), and c= 14.317 (4)Å, α= 110.72(2), β= 93.50(3), and γ= 113 08(3)°.