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- Title
[Ni(NHC)<sub>2</sub>] as a Scaffold for Structurally Characterized trans [H−Ni−PR<sub>2</sub>] and trans [R<sub>2</sub>P−Ni−PR<sub>2</sub>] Complexes.
- Authors
Sabater, Sara; Schmidt, David; Schmidt, Heidi; Kuntze‐Fechner, Maximilian W.; Zell, Thomas; Isaac, Connie J.; Rajabi, Nasir A.; Grieve, Harry; Blackaby, William J. M.; Lowe, John P.; Macgregor, Stuart A.; Mahon, Mary F.; Radius, Udo; Whittlesey, Michael K.
- Abstract
The addition of PPh2H, PPhMeH, PPhH2, P(para‐Tol)H2, PMesH2 and PH3 to the two‐coordinate Ni0 N‐heterocyclic carbene species [Ni(NHC)2] (NHC=IiPr2, IMe4, IEt2Me2) affords a series of mononuclear, terminal phosphido nickel complexes. Structural characterisation of nine of these compounds shows that they have unusual trans [H−Ni−PR2] or novel trans [R2P−Ni−PR2] geometries. The bis‐phosphido complexes are more accessible when smaller NHCs (IMe4>IEt2Me2>IiPr2) and phosphines are employed. P−P activation of the diphosphines R2P−PR2 (R2=Ph2, PhMe) provides an alternative route to some of the [Ni(NHC)2(PR2)2] complexes. DFT calculations capture these trends with P−H bond activation proceeding from unconventional phosphine adducts in which the H substituent bridges the Ni−P bond. P−P bond activation from [Ni(NHC)2(Ph2P−PPh2)] adducts proceeds with computed barriers below 10 kcal mol−1. The ability of the [Ni(NHC)2] moiety to afford isolable terminal phosphido products reflects the stability of the Ni−NHC bond that prevents ligand dissociation and onward reaction.
- Subjects
PHOSPHINE; MOIETIES (Chemistry); PHOSPHINES; LIGANDS (Chemistry)
- Publication
Chemistry - A European Journal, 2021, Vol 27, Issue 52, p13221
- ISSN
0947-6539
- Publication type
Article
- DOI
10.1002/chem.202101484