Vinylidene Complex Chemistry and Catalysis

Vinylidene complexes, in which an alkyne fragment binds to a transition metal centre and rearranges into an M=C=CHR motif, have emerged as versatile intermediates and catalysts in organometallic chemistry. The unique electronic structure of the vinylidene ligand, featuring a formal metal–carbon double bond conjugated to a substituted alkene, endows these species with both nucleophilic and electrophilic character. Such ambiphilicity enables diverse reactivity, including migratory insertions, protonations, cycloadditions and cross‐coupling processes. Key developments have focused on ruthenium and rhenium systems, which have demonstrated high turnover numbers in olefin metathesis, allylation and hydrometallation reactions. Computational studies have provided insight into the bonding and reactivity of vinylidene complexes, guiding the design of ligands that modulate catalyst stability, selectivity and activity. Beyond fundamental interest, applications span fine‐chemical synthesis, pharmaceutical intermediates and functional materials, underscoring the global significance of vinylidene‐mediated catalysis.

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Vinylidene Complex Chemistry and Catalysis publication trend

The graph below shows the total number of articles in vinylidene complex chemistry and catalysis across all publications each year (not limited to Nature Index journals).

Technical terms

Vinylidene complex: An organometallic species in which an alkyne has undergone rearrangement to form a metal–carbon–carbon linkage of the type M=C=CHR, featuring a double bond between the metal and the terminal carbon.

Vinylcarbenoid: A reactive intermediate derived from a vinylidene complex, in which the metal–carbon multiple bond displays increased carbenoid character, facilitating migratory insertions and nucleophilic additions.

Electrophilic fluorination: A transformation that introduces a fluorine atom into an organic or organometallic substrate via an electrophilic reagent, often proceeding through outer‐sphere mechanisms to achieve high regio- and stereocontrol.

References

1. Access to novel fluorovinylidene ligands via exploitation of outer-sphere electrophilic fluorination: new insights into C–F bond formation and activation. Dalton Transactions (2016).
2. Catalytic vinylogous cross-coupling reactions of rhenium vinylcarbenoids. Chemical Science (2018).