Eclipsed- and Staggered-[GePd{EPr}] (E = Si, Sn): Positional Isomerism in Deltahedral Zintl Clusters.

We report the synthesis and characterization of the cluster anions [GePd{SiPr}] (1) with a core of face-fused twinned icosahedra, GePd, and two sets of three PrSi-substituents positioned in "eclipsed" geometry. The new anion is a positional isomer of the recently reported "staggered" stannyl-ligated counterpart [GePd{SnPr}] (2), showing the possibility to find such positional isomerism in Zintl clusters. Both anions are characterized by single-crystal X-ray diffraction, H and C NMR, and negative-ion ESI-MS.

A Stannyl-Decorated Zintl Ion [Ge18Pd3(Sn(i)Pr3)6](2-): Twinned Icosahedron with a Common Pd3-Face or 18-Vertex Hypho-Deltahedron with a Pd3-Triangle Inside.

We report the synthesis and characterization of the title anion which has a germanium/palladium cluster core of [Ge18Pd3] and six tri-isopropyl tin substituents. Its two Ge9-halves are the first examples of germanium deltahedra with three nonsilyl substituents, tri-isopropyl tin in this case. The new cluster is made by a reaction of an acetonitrile suspension of K4Ge9 with (i)Pr3SnCl that generates primarily tristannylated 9-atom clusters [Ge9{Sn(i)Pr3}3](-), followed by addition of Pd(PPh3)4 to the reaction mixture.

Cluster Fusion: Face-Fused Nine-Atom Deltahedral Clusters in [Sn14 Ni(CO)](4.).

The title anion was synthesized by heating dimethylformamide (DMF) solution of the known Ni-centered and Ni(CO)-capped tin clusters [Ni@Sn9 Ni(CO)](3-) . The new anion represents the first example of face-fused nine-atom molecular clusters. The two clusters are identical elongated tricapped trigonal prisms of nido-[Sn8 Ni(CO)](6-) with nickel at one of the capping positions.

[Bi12Ni7(CO)4](4-): Aggregation of Intermetalloid Clusters by Their Thermal Deligation and Oxidation.

Reported are the synthesis and structure of the anionic intermetalloid cluster [Bi12Ni7(CO)4](4-). It was synthesized from the known smaller clusters Bi3Ni4(CO)6(3-), Bi3Ni6(CO)9(3-), and Ni@Bi6Ni6(CO)8(4-) by their aggregation as a result of thermal deligation and oxidation. The new cluster is structurally characterized by single-crystal X-ray diffraction in the compound (K[crypt])4[Bi12Ni7(CO)4] (1), and its presence in solution is confirmed by electrospray mass spectrometry.

Bi73-: the missing family member, finally isolated and characterized.

The synthesis and structure of Bi(7)(3-), the only missing member of the family of heptanuclear pnictogen cluster anions Pn(7)(3-) (Pn = pnictogen, a group 15 element excluding the unique nitrogen), is reported. The new species is synthesized by oxidation of a solution of K(5)Bi(4) by the solvent pyridine in the presence of (C(6)H(6))Cr(CO)(3). The existence of the species in solution is confirmed by electrospray mass spectrometry, while its structure is elucidated by single-crystal X-ray diffraction in the compound [K(2,2,2-crypt)](3)Bi(7)·2py (monoclinic, P2(1)/n, a = 13.