Further studies into the reactivity and coordination chemistry of [Ge9]4− Zintl ions. The indium-containing anions [In(Ge9)2]5−, [(Ge9)2In(C6H5)]4− and [Ge9{In(C6H5)3}2]4−

Abstract: Reactions between ethylenediamine solutions of K4Ge9 and triphenylindium yielded three novel Zintl ions, [In(Ge9)2]5− (1), [(Ge9)2In(C6H5)]4− (2), and [Ge9{In(C6H5)3}2}]4− (3). Species 1 exhibits an indium metal atom coordinated by two nine-atom germanium cages which bond to the central metal in an η 3-mode. The “staggered” arrangement of the two clusters confers the indium metal centre an octahedral coordination geometry. Species 2 displays trigonal planar coordination around the indium atom with an [In(C6H5)]2+ moiety acting as a bridge between the two halves of a [Ge9–Ge9]6− dimer. Finally, species 3 is composed of a [Ge9]4− deltahedral Zintl ion acting as a Lewis base to two In(C6H5)3 moieties. All three anions were characterized in the solid-state by single-crystal X-ray diffraction in [K(2,2,2-crypt)]5[1]·2en, [K(2,2,2-crypt)]4[2]·3tol and [K(2,2,2-crypt)]4[3], respectively. The existence of the anions in solution was confirmed by electrospray mass-spectrometry. DFT level calculations were also conducted on all of the cluster anions. [Copyright &y& Elsevier]