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Halogenation of Alkenes in Five‐Coordinate Platinum(II) Complexes – A Route to Stable (β‐Haloalkyl)platinum(IV) Species
Author(s) -
Fanizzi Francesco Paolo,
Maresca Luciana,
Pacifico Concetta,
Natile Giovanni,
Lanfranchi Maurizio,
Tiripicchio Antonio
Publication year - 1999
Publication title -
european journal of inorganic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.667
H-Index - 136
eISSN - 1099-0682
pISSN - 1434-1948
DOI - 10.1002/(sici)1099-0682(199908)1999:8<1351::aid-ejic1351>3.0.co;2-n
Subject(s) - chemistry , platinum , halogenation , olefin fiber , halogen , propene , medicinal chemistry , bromine , bromide , metal , stereochemistry , inorganic chemistry , catalysis , organic chemistry , alkyl
Five‐coordinate complexes [PtX 2 (olefin)(2,9‐Me 2 ‐phen)] ( 1 ; 2,9‐Me 2 ‐phen = 2,9‐dimethyl‐1,10‐phenanthroline; olefin = ethene denoted by a , propene by b , 1‐butene by c ; × = Cl denoted by x , Br by y ) undergo photoactivated reactions with Cl 2 and Br 2 to give the (β‐haloalkyl)platinum(IV) complexes [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 2axy containing the bromide, the bromoalkyl, and the phenanthroline ligands in the equatorial plane and two chloride ions in axial positions. The iodo complexes 1 ( a – c ) z are not oxidized by iodine even under UV irradiation but 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‐haloalkyl)platinum complex, has been determined by X‐ray diffraction methods. The stereochemistry of the (β‐haloalkyl)platinum(IV) complexes is in accord with a simultaneous addition of two halogen atoms to the coordinated olefin and to the metal center.