Addition of H2 Across a Cobalt–Phosphorus Bond. Issue 6 (11th January 2018)

• Record Type: Journal Article
• Authors: Poitras, Andrew M.; Knight, Sadie E.; Bezpalko, Mark W.; Foxman, Bruce M.; Thomas, Christine M.
• Is Part Of: Angewandte Chemie international edition. Volume 57:Issue 6(2018)
• Page Start: 1497
• Page End: 1500
• Publication Date: 2018-01-11
• Subjects: cobalt -- hydrides -- hydrogen -- phosphorus -- tridentate ligands; Chemistry -- Periodicals; 540
• DOI: 10.1002/anie.201710100
• Languages: English
• ISSNs: 1433-7851

Abstract

Abstract: Addition of H2 across the cobalt–phosphorus bond of (PPP)CoPMe3 (3 ) is demonstrated, where PPP is a monoanionic diphosphine pincer ligand with a central N‐heterocyclic phosphido (NHP − ) donor. The chlorophosphine Co II complex (PP Cl P)CoCl2 (2 ) can be generated through coordination of the chlorophosphine ligand (PP Cl P, 1 ) to CoCl2 . Subsequent reduction of2 with KC8 in the presence of PMe3 generates (PPP)CoPMe3 (3 ), in which both the phosphorus and cobalt centers have been reduced. The addition of 1 atm of H2 to complex3 cleanly affords (PP H P)Co(H)PMe3 (4 ), in which H2 has ultimately been added across the metal–phosphorus bond. Complex4 was characterized spectroscopically and using computational methods to predict its geometry. Abstract : Metal–phosphorus ligand cooperativity : A coordinatively unsaturated cobalt N‐heterocyclic phosphido complex is generated under reducing conditions. In an unusual example of a metal–phosphorus bifunctional σ‐bond cleavage process, the cobalt phosphide complex is found to readily add dihydrogen across the cobalt–phosphorus bond to generate new Co−H and P−H bonds.