Organonickel(II) Complexes with Anionic N-Donor Ligands. Hydration of coordinated nitriles at a nickel(II) site

The hydroxo complex (Bu4N)2[Ni2(C6F5)4(μ‐OH)2]reacts with 2,3,4,5,6‐pentafluoro benzenamine (C6F5‐NH2), 1,3‐diaryltriaz‐1‐enes (ArNHN=NAr, Ar = Ph, 4‐MeC6H4, 4‐MeOC6H4), 7‐aza‐1H‐indole (= 1H‐pyrrolo[2.3‐b]pyridine; Hazind), N‐phenylpyridin‐2‐amine(pyNHPh), and N‐phenylpyridine‐2‐carboxamide (py‐CONHPh) at room temperature in acetone to give the binuclear complexes (Bu4N)2[Ni2(C6F5)4(μ‐C6F5NH)2] (1) and (Bu4N)2[{Ni(C6F5)2} 2(μ‐OH)(μ‐azind)] (2) and the mononuclear complexes Bu4N[Ni(C6F5)2(ArN3Ar)] (3–5), Bu4N[Ni(C6F5)2(pyNPh)] (6), and Bu4N[Ni(C6F5)2(pyCONPh)] (7). The hydroxo.complex (Bu4N)2[{Ni(C6F5)2‐(μ‐OH)}2] promotes the nucleophilic addition of water to pyridine‐2‐carbonitrile, 2‐aminoacetonitrile, and 2‐(dimethylamino)acetonitrile, and complexes 8–10 containing pyridine‐2‐carboxamidato, 2‐aminoacetamidato and 2‐(dimethylamino)acetamidato ligands are formed. Analytical (C, H, N) and spectroscopic (IR, 1H and 19F‐NMR, and FAB‐MS) data were used for structural assignments. A single‐crystal X‐ray diffraction study of (Bu4N)2[{Ni(C6F5)2}2(μ‐OH)(μ‐azind)] (2) established the binuclear nature of the anion; the two Ni‐atoms are bridged by an OH group and a 7‐aza‐7H‐indol‐7‐yl group, but the central NiONiNCN ring is not planar, the dihedral angle between the NiONi and NiNCNNi planes being 84.4°.