[[abstract]]The reaction of E（E = Se, Te）with Cr(CO)6、Fe(CO)5 in highly concentrated KOH / MeOH solution at room temperature produces the trigonal bipyramidal cluster compounds [PPN]2[E2Cr2Fe(CO)10] ( E = Se, Te). On the other hand, Se reacts with Cr(CO)6、Fe(CO)5 in highly concentrated NaOH / MeOH solution gives the new compound [PPN]2[Se2Cr2Fe2(CO)12], which displays an octahedral core geometry. Reaction of E ( E = Se, Te) with Mo(CO)6、Fe(CO)5 in KOH / MeOH solution at 70 oC produces the octahedral cluster compounds [PPh4]2[E2Mo2Fe2(CO)12] (E = Se, Te). In the Se system, using NaOH / MeOH under the similar conditions, we obtain the octahedral compound [PPh4]2[Se2Mo2Fe2(CO)12] and another new octahedral product [PPh4]2[Se2MoFe3(CO)11] . Utilizing EO32- instead of E powder（E = Se, Te）, we obtain the same E2Mo2Fe2 (E = Se, Te) octahedral clusters from the reactions with Mo(CO)6 and Fe(CO)5. In the case of SeO32-, the reaction requires a milder condition; however, in the case of TeO32-, the reaction needs prolonged heating, both with the formation of unknown green compounds. In summary, a new synthesis and isolation of group 16 (E = Se, Te) containing mixed transition metal carbonyl clusters is developed. Further extension to other mixed metal system is promising.
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