Structure-Reactivity Correlations for the Dissociative Uncatalyzed Isomerization of...

Complexes of the type cis-[PtL(2)Me(2)] (1-14) (L = an extended series of phosphines of widely different steric and electronic properties) were synthesized, characterized, and used as precursors for the formation of cis-monoalkylplatinum(II) solvento species in methanol. The cleavage of the first platinum-alkyl bond by protonolysis is a fast process, but the subsequent cis to trans isomerization of the cationic solvento species [PtL(2)(Me)(MeOH)](+) is relatively slow and it can be( )()monitored using (31)P NMR or conventional spectrophotometry. A large collection of (1)H and (31)P NMR data for cis-[PtL(2)Me(2)], cis-[PtL(2)Me(MeOH)](+), and trans-[PtL(2)Me(MeOH)](+) complexes showed interesting dependencies upon the size, the sigma-donor capacity, and the mutual position of the phosphines in the coordination sphere of the metal. The rate constants for isomerization of cis-[PtL(2)Me(MeOH)](+) were resolved quantitatively into steric and electronic contributions of the phosphine ligands, by means of correlations with parameters which reflect their sigma-donor ability (chi values) and steric requirements (Tolman's cone angles, theta). The electronic and steric profiles obtained for these reactions are discussed within the framework of a mechanism which involves dissociative loss of the solvent molecule and interconversion of two geometrically distinct 3-coordinate T-shaped 14-electron intermediates. The factors controlling the stability of these coordinatively unsaturated species are discussed. The electronic and steric influences of phosphines as "spectator" ligands in a dissociative process are compared with those shown by these ligands when used as nucleophiles in associative substitution processes. The activation parameters DeltaH() and DeltaS() were measured using both conventional isothermal and non-isothermal spectrophotometric kinetics.