New Insights into the Stoichiometric and Catalytic Reactivity of Unsaturated Pd 3 (dppm) 3 CO n + Clusters ( n = 0, 1) Towards Halocarbons – First Evidence for Inorganic By‐Products

The title clusters, Pd 3 (dppm) 3 (CO) + and Pd 3 (dppm) 3 (CO) 0 can be electrochemically generated from the 1- and 2-electron reductions, respectively, of the Pd 3 (dppm) 3 (CO) 2 + cluster [dppm = bis(diphenylphosphanyl)methane; Pd 3 2 + ]. Pd 3 + reacts in a stoichiometric ratio with methyl iodide, MeI, and benzyl bromide, BzBr, in THF to provide the corresponding Pd 3 (X) + adducts (X = I, Br respectively) as inorganic products. Other products are Bz 2 and PhMe for BzBr but, for MeI, no organic product was observed (since they are too volatile). In the presence of the same substrates, Pd 3 0 also reacts in a stoichiometric ratio to form the same organics and the Pd 3 -(X) + adducts (X …