Mechanism of octahedral substitutions in nonaqueous media. Part VIII. Replacement of chloride by nucleophiles in trans-chloro(L)bis(ethylenediamine)cobalt(III) complexes in methanol

Abstract

The dependence of the rate of replacement of chloride by thiocyanate, azide, and nitrite in trans-[Co(en)₂LCl]ⁿ⁺ ion on L (L = NO₂, N₃, CN, Cl, and NCS) is the same in methanol as in water. The rate of replacement of chloride by methoxide in trans-[Co(en)₂LCl]ⁿ⁺ is faster for L = CN than for L = NO₂, as was the rate of replacement of chloride by hydroxide in base hydrolysis. The effects of L on rates are discussed.

The replacement of chloride by nitrite in trans-chlorocyanobis(ethylenediamine)cobalt(III) ion in methanol proceeds with retention of configuration as was shown by preparation of trans-cyanonitrobis(ethylenediamine)-cobalt(III) perchlorate.