Syntheses and properties of molecular nickel(II) hydride, methyl, and nickel(I) complexes supported by trimethylphosphane and (2-diphenylphosphanyl)thiophenolato and -naphtholato ligands

• Published in: Journal of organometallic chemistry Vol. 694; no. 12; pp. 1869 - 1876
• Main Authors: Kraikivskii, Peter B., Frey, Markus, Bennour, Hamdi A., Gembus, Armin, Hauptmann, Ralf, Svoboda, Ingrid, Fuess, Hartmut, Saraev, Vitaly V., Klein, Hans-Friedrich
• Format: Journal Article
• Language: English
• Published: Elsevier B.V 15-05-2009
• Subjects: Chelates; Nickel; P,S Ligands; Structure elucidation; P,S Ligands; Nickel; Chelates; Structure elucidation
• ISSN: 0022-328X; 1872-8561
• DOI: 10.1016/j.jorganchem.2009.01.023

Syntheses of hydrido and methylnickel complexes containing monoanionic P,S ligands are described. Spontaneous elimination of dihydrogen from hydridonickel functions proceeds with formation of molecular nickel(I) complexes.
(2-Diphenylphosphanyl)thiophenol (P^pSH) or (3-diphenylphosphanyl)-2-thionaphthol (P^nSH) react with Ni(PMe
3)
4 to form NiH(P^pS)(PMe
3)
2 (
1) or NiH(P^nS)(PMe
3)
2 (
2). 1,3-Bis(diphenylphosphanyl)propane (P^P) replaces the monodentate phosphane ligands to give NiH(P^pS)(P^P) (
3). NiMe(OMe)(PMe
3) or NiMe
2(PMe
3)
3 react with P^pSH to form NiMe(P^pS)(PMe
3) (
4) and NiMe(P^pS)(PMe
3)
2 (
5), respectively, and P^nSH affords NiMe(P^nS)(PMe
3)
2 (
6), NiMe(P^nS)(PMe
3) (
7). Dissociation of PMe
3 ligands induces transformation of
1 to Ni(P^pS)(PMe
3)
2 (
8) and Ni(P^pS)
2. Crystal and molecular structures are given for
1,
5–
8, and dynamic solution spectra (NMR, EPR) are discussed.