Organozinc Derivatives of Deltahedral Zintl Ions: Synthesis and Characterization of closo-[E9Zn(C6H5)]3- (E = Si, Ge, Sn, Pb)

Reactions of group 14 deltahedral Zintl ions E 9 4 - (E = Si, Ge, Sn, Pb) with diphenylzinc yielded the organically functionalized heteroatomic closo -clusters [E 9 Zn-Ph] 3 - (E = Si ( 1 ), Ge ( 2 ), Sn ( 3 ), Pb ( 4 )). All four clusters exhibit the same bicapped square antiprismatic geometry in which one of the capping positions is occupied by the ZnPh organometallic fragment. Three filled molecular orbitals of the cluster overlap with three empty orbitals at the ZnPh fragment, and the cluster acts as a six-electron ligand analogous to cyclopentadienyl and benzene ligands. The species were characterized by single-crystal X-ray diffraction in [K(2,2,2-crypt)] 3 [Si 9 Zn(C 6 H 5 )]·2py, [K(2,2,2-crypt)] 3 [Ge 9 Zn(C 6 H 5 )]·2en·tol, [K(2,2,2-crypt)] 3 [Sn 9 Zn(C 6 H 5 )]·tol, and [K(2,2,2-crypt)] 6 [Pb 9 Zn(C 6 H 5 )] 2 ·2en·tol. The presence of these clusters in solution was confirmed by electrospray mass spectrometry and 13 C{ 1 H} NMR experiments.