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

The hydroxo complex (Bu 4 N) 2 [Ni 2 (C 6 F 5 ) 4 (μ‐OH) 2 ]reacts with 2,3,4,5,6‐pentafluoro benzenamine (C 6 F 5 ‐NH 2 ), 1,3‐diaryltriaz‐1‐enes (ArNHN=NAr, Ar = Ph, 4‐MeC 6 H 4 , 4‐MeOC 6 H 4 ), 7‐aza‐1 H ‐indole (= 1 H ‐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 (Bu 4 N) 2 [Ni 2 (C 6 F 5 ) 4 (μ‐C 6 F 5 NH) 2 ] ( 1 ) and (Bu 4 N) 2 [{Ni(C 6 F 5 ) 2 } 2(μ‐OH)(μ‐azind)] ( 2 ) and the mononuclear complexes Bu 4 N[Ni(C 6 F 5 )2(ArN 3 Ar)] ( 3 – 5 ), Bu 4 N[Ni(C 6 F 5 ) 2 (pyNPh)] ( 6 ), and Bu 4 N[Ni(C 6 F 5 ) 2 (pyCONPh)] ( 7 ). The hydroxo.complex (Bu 4 N) 2 [{Ni(C 6 F 5 )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, 1 H and 19 F‐NMR, and FAB‐MS) data were used for structural assignments. A single‐crystal X‐ray diffraction study of (Bu 4 N) 2 [{Ni(C 6 F 5 ) 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‐7 H ‐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°.