Vapor Phase Installation of CpCo(CO) 2 in MOF‐808

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Abstract Metal‐organic frameworks (MOFs), including MOF‐808 present an opportunity for vapor phase installation of reactive centers that may serve as uniform sites for precision catalysis. The mechanism of cobalt installation in MOF‐808 through atomic layer deposition (ALD) upon CpCo(CO) 2 exposure is investigated through in situ FTIR spectroscopy complemented by density functional theory modeling. The role of subsequent H 2 O exposure in the hydrolysis of carbonyl and cyclopentadienyl ligands to complete the installation is also investigated. In situ FTIR study reveals that upon exposure of CpCo(CO) 2 to MOF‐808 at 115 °C, a long‐lived, stable intermediate is formed that presents carbonyl stretching vibrations similar to the undissociated precursor that are attributed to multiple chemisorbed carbonyl complexes. In MOF‐808, cobalt species are initially absorbed near the BTC linker rather than directly on the nodes, revealing the importance of non‐covalent interactions in the installation process. DFT suggests that H 2 O exposure promotes carbonyl elimination but leaves a cyclopentadienyl‐capped cobalt that is more stable than the complete hydrolysis product. The simulations are consistent with cobalt installation in MOF‐808 using CpCo(CO) 2 and H 2 O at 115 °C and further consistent with the lack of ALD thin film deposition of cobalt oxide thin films on planar supports.

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