摘要:
The aminoindenyl complexes {Ind(CH2)(3,4)N(t-Bu)H}Ni(PPh3)Cl (7, 8) and {Ind(CH2)(2,3)NMe2}Ni(PPh3)Cl (9, 10) have been prepared and characterized by spectroscopy and, in the case of 7 and 9, by X-ray structural studies. Although there is no interaction between the Ni center and the amine moiety of these complexes in the solid state, solution spectra point to a temperature-dependent, intramolecular N-->Ni coordination in complex 9 and a more facile, intermolecular interaction in 10. Abstraction of Cl- from these complexes led to the formation of the cations [{eta(3):eta(0)-Ind(CH2)(3,4)N(t-Bu)H}Ni(PPh3)(2)](+) and [{eta(3):eta(1)-Ind(CH2)(2,3)NMe2}Ni(PPh3)](+) (11, 12). The origin of the observed differences in the reactivities of these complexes is discussed in terms of the lengths of the tether and the nature of the N-substituents.