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The calix[4]arene molybdenum imido complex [CaxO4Mo(NtBu)] (1) reacts with HCl to give, in a reversible reaction, the 1,2-addition product [Cax(OH)O3Mo(NtBu)Cl] (4). Reaction with PhICl2 does not lead to scission of the imido group either, but results in an unprecedented 1,6-addition of chlorine to the metallocalixarene to give a molybdenum 4-chloro-2,5-cyclohexadienone complex [CaxClO4Mo(NtBu)Cl] (5), which has been structurally characterized. This compound is the first example of a structurally characterized 4-halo-2,5-cyclohexadienone transition metal complex.
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Radius et al. (2002) studied this question.
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