The progressive addition of anhydrous pyridine, (py), to a solution of [Rh4(CO)12] in CH2Cl2 under CO, even at low temperature, results in immediate disproportionation to give cis-[Rh(CO)2py2][Rh5(CO)15]; further addition of pyridine results in the progressive replacement of CO’s by py on the same apical rhodium in [Rh5(CO)15]− to give cis-[Rh(CO)2py2][Rh5(CO)15−xpyx] (x = 1, 2). The analogous reactions with 2,2′-bipyridine (bipy) give only [Rh(CO)2bipy][Rh5(CO)13bipy]. IR and low temperature, multinuclear NMR measurements have been used to establish the structures of all the above anions and the structures of [Rh5(CO)13(bipy)]− and [Rh5(CO)13py2]− are subtly different. Under N2, [Rh4(CO)12] reacts with py to give [Rh6(CO)16−ypyy] (y = 1, 2).
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