Kinetics of reactions of Os6(CO)18 with some P-donor nucleophiles: Some unusual isokinetic relationships

The cluster Os6(CO)18 with its bi-capped tetrahedral Os6 core reacts with some P-donor nucleophiles in toluene via associative paths, but the range of P-donors that can react at convenient rates for kinetic study is limited by the exceptional dependence of the rates on the basicity and size of the nucleophiles. The observed linear free energy relationship (LFER), shown by the small set of accessible data is accompanied by the existence of an …