Abstract
The reaction of Fe(CO) 5 with HgCl 2 proceeds via the consecutive reactions Fe(CO) 5 + 2 HgCl 2 → cis-Fe(CO) 4 (HgCl) 2 + COCl 2 (a) cis-Fe(CO) 4 (HgCl) 2 + 2 HgCl 2 → cis-Fe(CO) 4(HgCl · HgCl 2) 2 (b) a and b. The kinetics and mechanism of the two processes have been tsudied. They have been found to obey the rate laws: d[Fe(CO) 5]/d t k a[Fe(CO) 5] [HgCl 2] 2 d[ cis-Fe(CO) 4(HgCl) 2]/d t k b[ cis-Fe(CO) 4(HgCl) 2][HgCl 2] 2 The mechanism for process a is inferred to be similar to that observed for other oxidative addition—elimination reactions, involving the successive formation of 1/1 and 1/2 “adducts” of Fe(CO) 5 and HgCl 2, and other rapid steps. Analogies between this mechanism and those of reactions involving the fixation of molecular nitrogen are discussed. The mechanism of reaction b, and activation parameters for each path are presented and discussed.
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