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Highly Selective Hydroboration of Terminal Alkenes Catalyzed by a Cobalt Pincer Complex Featuring a Central Reactive N-Heterocyclic Phosphido Fragment

https://doi.org/10.1021/acs.organomet.0c00741

Poitras, Andrew M.; Oliemuller, Leah K.; Hatzis, Gregory P.; Thomas, Christine M. (April 2021, Organometallics)
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N‐Heterocyclic Phosphido Complexes of Rhodium Supported by a Rigid Pincer Ligand

https://doi.org/10.1002/ejic.202000390

Hatzis, Gregory P.; Oliemuller, Leah K.; Dickie, Diane A.; Thomas, Christine M. (August 2020, European Journal of Inorganic Chemistry)
A Series of Dimeric Cobalt Complexes Bridged by N-Heterocyclic Phosphido Ligands

https://doi.org/10.1021/acs.inorgchem.9b03790

Poitras, Andrew M.; Bezpalko, Mark W.; Moore, Curtis E.; Dickie, Diane A.; Foxman, Bruce M.; Thomas, Christine M. (April 2020, Inorganic Chemistry)

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Cooperative activation of O–H and S–H bonds across the Co–P bond of an N-heterocyclic phosphido complex

https://doi.org/10.1039/C8DT05052J

Poitras, Andrew M.; Bezpalko, Mark W.; Foxman, Bruce M.; Thomas, Christine M. (February 2019, Dalton Transactions)

Metal–ligand cooperation has proven to be a viable concept for σ bond activation and catalysis, however there are few examples involving phosphorus as an active participant in bond cleavage. The reactivity of E–H bonds (E = S, O) across a metal–phosphorus bond of a cobalt( i ) center ligated by a tridenate N-heterocyclic phosphido (NHP − ) ligand with diphosphine sidearms, (PPP) − , has been explored. Addition of PhOH to (PPP)CoPMe 3 ( 1 ) cleanly affords (PP OPh P)Co(H)PMe 3 ( 2 ), in which the O–H bond was heterolytically cleaved across the M–P NHP bond. Addition of PhSH to 1 first generates (PP H P)Co(SPh)PMe 3 ( 3 ), which undergoes an intermolecular rearrangement to generate (PP SPh P)Co(H)PMe 3 ( 4 ) as the thermodynamic product. A comparison with a related platinum( ii ) system reveals the subtle effects that variations in metal intrinsic properties can have on metal–ligand bifunctional σ bond activation processes.
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