Metallacyclopentadienes: synthesis, structure and reactivity.

Metallacyclopentadienes, which possess two M-C(sp2) bonds and feature the structure of M(C[upper bond 1 start]R1[double bond, length as m-dash]CR2-CR3[double bond, length as m-dash]C[upper bond 1 end]R4), are an important class of five-membered metallacycles. They are considered as both reactive intermediates in the stoichiometric and catalytic transformations of organic molecules and useful precursors to main group element compounds, and have received considerable attention in organometallic chemistry, coordination chemistry and synthetic organic chemistry over the past six decades because of their unique metallacyclic structure. This review comprehensively presents the synthesis, structure and reactivity of the s-, p-, d- and f-block metallacyclopentadienes distributed in the whole periodic table. In addition, their application in synthetic organic chemistry and polymer chemistry is summarized. This review aims to be beneficial for the design and synthesis of novel metallacyclopentadienes, and for promoting the rapid development of metallacyclic chemistry.