Metal/Organosilicon Complexes: Structure, Reactivity, and Considerations for Catalysis

ABSTRACT

Complexes featuring metal–silicon bonds play a key role in many catalytic and stoichiometric transformations. As such, it is important to understand the underlying electronic structures of such units and the reactivity patterns they engender, which in many cases differ substantially from well-known patterns for metal–carbon bonds. This review seeks to provide a framework for understanding reactivity of metal/organosilicon units, focusing specifically on considerations for catalysis, similarities and differences between M–C and M–Si chemistry, and possibilities for M/Si cooperative catalysis.

Graphical abstract

KEYWORDS:

• Silane
• silylene
• silicon transition-metal complexes
• metal–ligand cooperation (MLC)

Acknowledgments

The authors acknowledge support from Carleton College, the Petroleum Research Fund administered by the American Chemical Society (grant 50980-UNI3 to MTW), the Camille & Henry Dreyfus Foundation, and the National Science Foundation (CHE-1552591 to MTW). Computational resources were provided by the Extreme Science and Engineering Discovery Environment (XSEDE), which is supported by the National Science Foundation (ACI-1548562). The authors also express appreciation to the many students from their laboratories whose discoveries and insights have helped shape their understanding of the nature of metal/silicon interactions.

Additional information

Funding

This work was supported by the American Chemical Society Petroleum Research Fund [50980-UNI3]; Camille and Henry Dreyfus Foundation [TH-16-035]; National Science Foundation [CHE-1552591].