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

(2-Diphenylphosphanyl)thiophenol (P^pSH) or (3-diphenylphosphanyl)-2-thionaphthol (P^nSH) react with Ni(PMe3)4 to form NiH(P^pS)(PMe3)2 (1) or NiH(P^nS)(PMe3)2 (2). 1,3-Bis(diphenylphosphanyl)propane (P^P) replaces the monodentate phosphane ligands to give NiH(P^pS)(P^P) (3). NiMe(OMe)(PMe3) or NiMe2(PMe3)3 react with P^pSH to form NiMe(P^pS)(PMe3) (4) and NiMe(P^pS)(PMe3)2 (5), respectively, and P^nSH affords NiMe(P^nS)(PMe3)2 (6), NiMe(P^nS)(PMe3) (7). Dissociation of PMe3 ligands induces transformation of 1 to Ni(P^pS)(PMe3)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.