Cooperative activation of O–H and S–H bonds across the Co–P bond of an N-heterocyclic phosphido complex (Electronic supplementary information (ESI) available: Spectroscopic characterization data for 2–4, crystallographic data collection and refinement details for 2, computational details, and XYZ coordinates of optimized geometries for 2–4. CCDC 1876919. For ESI and crystallographic data in CIF or other electronic format see DOI: 10.1039/c8dt05052j)

Andrew M Poitras; Mark W Bezpalko; Bruce M Foxman; Christine M Thomas

doi:10.1039/c8dt05052j

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Cooperative activation of O–H and S–H bonds across the Co–P bond of an N-heterocyclic phosphido complex (Electronic supplementary information (ESI) available: Spectroscopic characterization data for 2–4, crystallographic data collection and refinement details for 2, computational details, and XYZ coordinates of optimized geometries for 2–4. CCDC 1876919. For ESI and crystallographic data in CIF or other electronic format see DOI: 10.1039/c8dt05052j)

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Cooperative activation of O–H and S–H bonds across the Co–P bond of an N-heterocyclic phosphido complex (Electronic supplementary information (ESI) available: Spectroscopic characterization data for 2–4, crystallographic data collection and refinement details for 2, computational details, and XYZ coordinates of optimized geometries for 2–4. CCDC 1876919. For ESI and crystallographic data in CIF or other electronic format see DOI: 10.1039/c8dt05052j)

Andrew M Poitras, Mark W Bezpalko, Bruce M Foxman and Christine M Thomas

Dalton transactions : an international journal of inorganic chemistry, Vol.48(9), pp.3074-3079

01/01/2019

DOI: https://doi.org/10.1039/c8dt05052j

PMID: 30758361

Abstract

Hydrogen bonds

Phosphides

Platinum

Phosphorus

Activation

Catalysis

Covalent bonds

Data Acquisition

Ligands

Crystallography

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.

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Title: Cooperative activation of O–H and S–H bonds across the Co–P bond of an N-heterocyclic phosphido complex (Electronic supplementary information (ESI) available: Spectroscopic characterization data for 2–4, crystallographic data collection and refinement details for 2, computational details, and XYZ coordinates of optimized geometries for 2–4. CCDC 1876919. For ESI and crystallographic data in CIF or other electronic format see DOI: 10.1039/c8dt05052j)
Creators: Andrew M Poitras
Mark W Bezpalko
Bruce M Foxman
Christine M Thomas
Publication Details: Dalton transactions : an international journal of inorganic chemistry, Vol.48(9), pp.3074-3079
Publisher: Royal Society of Chemistry
Identifiers: 9923989472301921
Academic Unit: Department of Chemistry
Language: English
Resource Type: Journal article

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