[Ni(NHC)

Autor: Sara, Sabater, David, Schmidt, Heidi Née Schneider, Schmidt, Maximilian W, Kuntze-Fechner, Thomas, Zell, Connie J, Isaac, Nasir A, Rajabi, Harry, Grieve, William J M, Blackaby, John P, Lowe, Stuart A, Macgregor, Mary F, Mahon, Udo, Radius, Michael K, Whittlesey
Rok vydání: 2021
Předmět:
Zdroj: Chemistry (Weinheim an Der Bergstrasse, Germany)
ISSN: 1521-3765
Popis: 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.
Whole lotta terminal phosphidos: A combined experimental and computational study of the reactivity of [Ni(NHC)2] (NHC=N‐heterocyclic carbene) towards secondary and primary phosphines has been undertaken. P−H bond activation, as well as P−P activation of diphosphines, yields an extensive series of structurally characterised terminal phosphido complexes that exhibit unusual trans‐phosphido hydrido and novel trans‐bis‐phosphido geometries.
Databáze: OpenAIRE
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