Halogenation of Alkenes in Five-Coordinate Platinum(II) Complexes – A Route to Stable (β-Haloalkyl)platinum(IV) Species
✍ Scribed by Francesco Paolo Fanizzi; Luciana Maresca; Concetta Pacifico; Giovanni Natile; Maurizio Lanfranchi; Antonio Tiripicchio
- Publisher
- John Wiley and Sons
- Year
- 1999
- Tongue
- English
- Weight
- 323 KB
- Volume
- 1999
- Category
- Article
- ISSN
- 1434-1948
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✦ Synopsis
Five-coordinate complexes [PtX 2 (olefin)(2,9-Me 2 -phen)] (1; chloride ions in axial positions. The iodo complexes 1(a-c)z are not oxidized by iodine even under UV irradiation but 2,9-Me 2 -phen = 2,9-dimethyl-1,10-phenanthroline; olefin = ethene denoted by a, propene by b, 1-butene by c; X = Cl react readily with Cl 2 or Br 2 to give 2(a-c)x and 2(a-c)y. The structure of 2ay, the first structurally characterized (β-denoted by x, Br by y) undergo photoactivated reactions with Cl 2 and Br 2 to give the (β-haloalkyl)platinum(IV) complexes haloalkyl)platinum complex, has been determined by X-ray diffraction methods. The stereochemistry of the (β-[Pt(CH 2 CHRX)(2,9-Me 2 -phen)X 3 ] (2). Bromination of the chloro species 1ax leads to the formation of the Pt IV species haloalkyl)platinum(IV) complexes is in accord with a simultaneous addition of two halogen atoms to the 2axy containing the bromide, the bromoalkyl, and the phenanthroline ligands in the equatorial plane and two coordinated olefin and to the metal center.
in the propensity of these species to undergo β-elimination [a] Dipartimento Farmaco-Chimico, Universita `di Bari, [PtX 2 (olefin)(2,9-Me 2 phen)] (1) (2,9-Me 2 -phen ϭ 2,9-divia E. Orabona 4