Issue 9, 2019

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

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

Supplementary files

Article information

Article type
Paper
Submitted
21 dic. 2018
Accepted
06 feb. 2019
First published
07 feb. 2019

Dalton Trans., 2019,48, 3074-3079

Author version available

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, 48, 3074 DOI: 10.1039/C8DT05052J

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