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

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Abstract

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)CoPMe3 (1) cleanly affords (PPOPhP)Co(H)PMe3 (2), in which the O–H bond was heterolytically cleaved across the M–PNHP bond. Addition of PhSH to 1 first generates (PPHP)Co(SPh)PMe3 (3), which undergoes an intermolecular rearrangement to generate (PPSPhP)Co(H)PMe3 (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.

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

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Publication details

The article was received on 21 Dec 2018, accepted on 06 Feb 2019 and first published on 07 Feb 2019


Article type: Paper
DOI: 10.1039/C8DT05052J
Citation: Dalton Trans., 2019, Advance Article

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

    A. M. Poitras, M. W. Bezpalko, B. M. Foxman and C. M. Thomas, Dalton Trans., 2019, Advance Article , DOI: 10.1039/C8DT05052J

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