Sir:We wish to draw your attention to a recent paper' concerning the uncatalyzed cis to trans isomerization and methanol solvolysis of arylplatinum complexes. Romeo and coworkers' present arguments, in addition to those stated prev i o u~l y ,~-~ in favor of a dissociative mechanism (Scheme I) for the spontaneous isomerization and an associative mechanism for the solvolysis (halide substitution) of c~'s-Pt(PEt~)~-(R)X, where X an alkyl or Substituted aryl group. However, the reported eviden~el-~ is by no means conclusive, and a number of anomalies, which will be discussed, remain unsolved.Romeo and co-workers4 reported similar rate parameters for the uncatalyzed isomerization and methanol solvolysis of the most sterically crowded complex in the series (viz., R mesityl) and extended their arguments to favor a dissociative solvolysis mechanism for the latter complex. This is in contrast to the generally accepted associative mode of substitution for the complexes containing the less sterically crowded substituents in particular1g4 and for Pt(I1) complexes in general: The rate and activation Registry No. c~~-P~( P E~~)~( C~H~) I , 56553-44-7; c i~-P t ( P E t~)~-(C6H5)Br, 15702-94-0; c~~-P~( P E~~)~( C~H~) C I , 15702-92-8.
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