158792-01-9Relevant academic research and scientific papers
Phase dependent η2-alkene versus η1-alkyl transformation in platinum(II) complexes
Maresca, Luciana,Natile, Giovanni
, p. 301 - 304 (1999)
Addition products of some nucleophiles to the coordinated olefin in [Pt(η2-olefin)Cl(tmen)]+ (1) (tmen = N,N,N′,N′-tetramethylethylenediamine) have shown to undergo a chemical transformation in the solid phase. The acetylacetonate (a
CATIONIC COMPLEXES OF PLATINUM(II) WITH η2-OLEFINS: SYNTHESIS AND REACTIVITY OF THE ALKENE
Fanizzi, Francesco P.,Maresca, Luciana,Natile, Giovanni,Pacifico, Concetta
, p. 137 - 142 (2007/10/02)
New cationic olefin complexes of platinum(II), 2-olefin)X(tmen)>(ClO4) a; NO2, b.Tmen = N,N,N',N'-teramethylethylenediamine>, have been prepared by olefin metathesis from 1.Substitution of propene and styrene for ethene takes place with high yield of product, independent of the nature of X; in contrast, substitution of (E)- and (Z)-2-butene for ethene occurs only in the case of X = NO2.Complexes 2b and 5b gave evidence of a metallacycle formation promoted by nucleophilic attack of one oxygen of the nitro ligand onto the cis olefin, which shifts from η2 to η1 coordination.The olefin, in the cationic species, easily undergoes nucleophilic attack by OH-, MeO-, and acetylacetonate anions.In the case of unsymmetrically substituted olefins the addition reaction takes place with a high degree of regioselectivity according to Markovnikov's rule. 1H NMR data and, in particular, the JPt,H values have proved to be very valuable tools for determining the coordination mode of the carbon ligand and the configuration of the complexes.Acid cleavage of the products of carbon nucleophile addition was performed under different experimental conditions (gaseous HCl in chlorinated solvents or aqueous perchloric acid).The yield of Pt-C bond cleavage (and consequent alkylation of the carbon nucleophile) was greater in the chloride than in the nitro species and in aprotic than in protic media.
