Arylzinc Alkoxides: [ArZnOCHP ]2 and Ar2Zn3(OCHP )4 When Ar = C6H5, p-CF3C6H4, 2,4,6-Me3C6H2, and C6F5

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Abstract
From the reactions between diarylzinc compounds (Ar2Zn) and the alcohol (P CHOH) in toluene, the compounds [ArZn(OCHP )]2 (Ar = C6H5, C6F5, p-CF3C6H4, and 2,4,6-Me3C6H2) have been isolated and shown to exist in equilibra with the trinuclear complexes Ar2Zn3(OCHP )4 and Ar2Zn when Ar = C6H5, C6F5, and p-CF3C6H4. The trinuclear complexes have also been prepared from reactions of the Ar2Zn compounds with the alcohol, which reveals that the ease of Zn−C(aryl) bond cleavage is sensitive to the nature of the Ar group: C6H5 > 4-CF3C6H4 > C6F5. The molecular structures of Ar2Zn3(OCHP )4 where Ar = p-CF3C6H4 and C6F5 and [ArZn(OCHP )]2 where Ar = C6F5, p-CF3C6H4, and 2,4,6-Me3C6H2 are reported based on single-crystal X-ray diffraction studies. The X-ray structure of Zn(p-CF3C6H4)2 is also reported. The reactivity of these new compounds toward the polymerization of propylene oxide (PO) and the copolymerization of PO and CO2 have been investigated along with related reactions involving the partial hydrolysis of the Ar2Zn and R2Zn compounds, where R = t-Bu, n-Bu, and n-Oct. These results are compared with the previous studies employing Et2Zn as an organozinc precursor.