184764-29-2Relevant academic research and scientific papers
Rigid-rod polymers, oligomers, and model complexes with Pt-Pt bonds in the backbone
Irwin, Michael J.,Jia, Guochen,Vittal, Jagadese J.,Puddephatt, Richard J.
, p. 5321 - 5329 (1996)
Reaction of [Pt2Cl2(μ-dppm)2], dppm = Ph2PCH2PPh2, with PhC≡CH in methanol gives [Pt2Cl2(μ-dppm)2(μ-PhCCH)], 1, or, in the presence of base, [Pt2(C≡CPh)2(μ-dppm)2], 2, or [Pt2(C≡CPh)2(μ-dppm)2(μ-PhCCH)], 4. Complex 2 reacts with chlorinated solvents to reform [Pt2Cl2(μ-dppm)2], but in the presence of base, [Pt2(C≡CPh)2(μ-dppm) 2(μ-OH?Cl)], 3, may be formed. Complexes 1 and 3 have been characterized by X-ray structure determinations, and the conditions for formation of 2 have been optimized as a model reaction for polymer formation by using diacetylenes. Reaction of [Pt2Cl2(μ-dppm)2] with HC≡CArC≡CH in methanol in the presence of base gives insoluble oligomers characterized as Cl-[Pt2(μ-C≡CArC≡C)2(μ-dppm) 2]x[Pt2Cl(μ-dppm)2], 5, that is as a diacetylide bridged oligomer with chloride end groups; depending on the diacetylide used x varies from ca. 3-12. Cationic polymers [Pt2(μ-dppm)2(μ-L-L)]x(BF 4)2x, 6 or 7, are formed by reaction of [Pt2Cl2(μ-dppm)2] with diisocyanide ligands C≡NArN≡C or with the diphosphine ligand Ph2PC6H4PPh2, respectively. In contrast, the diphosphine ligand i-Pr2PC6H4C6H4P-i-Pr 2, having a longer spacer group, gives the cyclic complex [Pt2(μ-dppm)2(μ-i-Pr2PC6H 4C6H4P-i-Pr2)]2(BF 4)4. The polymeric complexes 5-7 are insoluble or sparingly soluble in common organic solvents. They represent rare examples of conjugated, rigid-rod oligomers or polymers with metal-metal bonds in the backbone.
