Synthesis And Reactivities Of Indenylnickel(Ⅱ) N-Heterocyclic Carbene Complexes

1. The cyclopentadienylnickel(II) and indenylnickel(II) complexes bearing N-heterocyclic carbenes [(Cp)Ni(NHC)X (X = Cl, Br) (1, 2, 3) and (l-R-Ind)Ni(NHC)X (R=H, X=C1, Br; R=Me, X=C1)](4, 5, 6, 7, 8) have been synthesized by the reactions of (Cp)₂Ni or (R-Ind)2Ni (R = H, Me) with the imidazolium salts, respectively. All of them have been characterized by elementary analysis, NMR, IR and melting point determination, Among them, 1, 4, 5, 6 have been characterized by single-crystal X-ray analysis.2. The further reactions of (Ind)Ni(NHC)X (4, 21) with another equivalent of corresponding imidazolium salts in refluxing toluene resulted in bis-NHC nickel(II) complexes (NHC)₂NiX₂(11, 12). Meanwhile, the bis-NHC nickel(II) complexes 10,11,12, 13, 14 also could be synthesized by the reactions of (R-Ind)₂Ni with two equivalent of imidazolium salts in refluxing toluene. All of them have been characterized by elementary analysis, NMR, IR and melting point determination, Among them, 10, 11 have been characterized by single-crystal X-ray analysis.3. The aryloxo complexes of (Cp)Ni(NHC)(OAr) (15, 16) and of (Ind)Ni(NHC) (OAr) (17, 18) have been synthesized by the aryloxylation reactions of the corresponding (Cp)Ni(NHC)X (1, 2, 3) and (1-R-Ind)Ni(NHC)X (4, 20, 21), respectively. All of them have been characterized by elementary analysis, NMR, IR and melting point determination, Among them, 15,18 have been characterized by single-crystal X-ray analysis.4. The indenyl-functionalized N-heterocyclic carbene ligand was first synthesized via the reaction of 1-(3-bromopropyl)-1H-indene with 1-isopropyl-imidazole. Furthermore, the first indenyl-functionalized N-heterocyclic carbene complex of nickel(II) (19) was...