Abstract
The high nuclearity carbonyl cluster (HNCC) Ru 6 C(CO) 17 has been shown to react with a wide variety of P-donor nucleophiles exclusively by associative processes. The rate constants, k 2 , can be subdivided into electronic and steric contributions which depend on the σ-donicity and size of the P-donor nucleophiles. The standard reactivity for a weak and small hypothetical nucleophile of pK a '=−4 is defined by log k 2 °=log k 2 2-β(pK a '+4) and shows an exceptionally high value of 1.51±0.26. The electronic sensitivity (β=0.41±0.04) is also very high and indicates a high degree of bond making in the transition state.
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