Abstract
Formal [3+2] cycloaddition reactions between the bis-sulfonium zirconocene-ate dimer ▪ 1a and methylpropiolate, benzaldehyde and carbon disulfide afforded stable zwitterionic phosphonium zirconocene-ate complexes 2– 4, respectively, with two orthocondensed five-membered heterocycles. X-ray crystal structure of 4 has been determined. Elemental chalcogens (S, Se, Te) gave rise also to a new variety of five-coordinate zirconium(IV) complexes ( 5– 7) by a formal [3+1] cycloaddition reaction. In these bicyclic zirconates, sulfur is included in a five-membered ring while the second chalcogen is in a four-membered one.
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