Substituent effects on associative reactions of the clusters Ru5C(CO)14L (L = P(OPh)3 and P(C6H11)3) with phosphorus-donor nucleophiles

The substitution reactions of the high-nuclearity carbonyl clusters Ru5C(CO)14L (L = P(OPh)3 and PCy3) with a series of P-donor nucleophiles in heptane have been shown to proceed readily by associative pathways. The effects of the different electronic and steric properties of the nucleophiles at 25°C can be separated quantitatively in a way that has been previously shown to be widely successful. Comparing the fastest and slowest reactions for L …