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 = 13.8739(13) Å, b = 24.878(2) Å, c = 26.401(2) Å, β = 96.353(4)°, V = 9056.5(14) Å(3), Z = 4, and R1/wR2 = 0.0636/0.1390 for the observed data and 0.0901/0.1541 for all data).

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. It was structurally characterized by single-crystal X-ray diffraction in [K(222crypt)]2[Ge18Pd3{Sn(i)Pr3}6]·(i)Pr2O and was also confirmed in solution by ESI-MS and NMR. The new anion can be viewed both as a dimer of face-fused icosahedra (twinned icosahedron) with a common Pd3-face, i.e., [((i)Pr3Sn)3Ge9Pd3Ge9(Sn(i)Pr3)3](2-) that resembles but is not isoelectronic with the known borane version B21H18(-) or as a large hypho-deltahedron of 18 Ge-atoms with a triangle of Pd3 inside, i.e., [Pd3@Ge18(Sn(i)Pr3)6](2-). DFT calculations show a very large HOMO-LUMO gap of 2.42 eV.

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. It can be viewed as composed of a Ni-centered icosahedral core of Bi6Ni6(CO)4 where two diametrically opposed Ni atoms are capped by Bi3 triangles. However, its electron count is rationalized based on a structure made of fused tetrahedra.

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 andC NMR, and negative-ion ESI-MS. Using relativistic DFT calculations, we elucidate and discuss the reasons for the different positioning of the ligands in the stannyl- and silyl-functionalized species.

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. They are fused along a triangular face adjacent to a trigonal prismatic base and made of two Sn and one Ni atoms. The new anion is structurally characterized by single-crystal X-ray diffraction in the compound (K[222-crypt])4 [Sn14 Ni(CO)]⋅DMF. Its presence in solution is corroborated by electrospray mass spectrometry.