Reaction of dimethylplatinum(II) complexes with PhCH2CH2Br: Comparative reactivity with CH3CH2Br and PhCH2Br and synthesis of Pt(IV) complexes

Oxidative addition of 2‐phenylethylbromide (PhCH 2 CH 2 Br) to dimethylplatinum(II) complexes [PtMe 2 (NN)] ( 1a , NN = 2,2′‐bipyridine (bpy); 1b , NN = 1,10‐phenanthroline (phen)) afforded the new organoplatinum(IV) complexes [PtMe 2 (Br)(PhCH 2 CH 2 )(bpy)], as a mixture of trans ( 2a ) and cis ( 3a ) isomers, and [PtMe 2 (Br)(PhCH 2 CH 2 )(phen)], as a mixture of trans ( 2b ) and cis ( 3b ) isomers, respectively. The new Pt(IV) complexes were readily characterized using multinuclear ( 1 H and 13 C) NMR spectroscopy and elemental microanalysis. The crystal structure of 2a was further determined using X‐ray crystallography indicating an octahedral geometry around the platinum centre. A comparison of reactivity of RCH 2 Br reagents (R = CH 3 , Ph or PhCH 2 ) in their oxidative addition reactions with complex 1a , with an emphasis on the effects of the R groups of alkyl halides, was also conducted using density functional theory.