Synthesis and Structure of the Metalated Zintl Ion [Ge_9(μ_(10)-Ge)Ni(PPh_3)]~(2-)

摘要

Since the discovery and subsequent investigation of the Group 14 Zintl ions, only a tew transition metal derivatives of these unusual clusters have been detected. The only structurally characterized examples, the tin and lead [closo-E_9Cr(CO)_3]~(4-)ions and the [Sn_6{Cr(CO)_5}_6]~(2-) ion, were made by two vastly different synthetic methods. Teixi-dor et al. characterized two Pt-E_9 species (E = Sn. Pb) by NMR spectroscopy; however, little is known about their structures. Even though there are several structurally characterized naked germanide ions (Ge_9~(n-) where n = 2, 3. or 4; Ge_(10)~(2n-)), complexes of the germanide Zintl anion with transition metals have not previously been described. Herein we report the synthesis and characterization of[K ([2,2,2]-cryptand)]_2[Ge,(μ_(10)-Ge)Ni(PPh_3)]-en (for [2,2,2]cryptand see [17], en = ethylenediamine), the first metalated germanide anion and only the second example of the rare nido-10 (iv + iv) structure type.