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

Abstract

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.

Insights into Formation and Relationship of Multimetallic Clusters: On the Way toward Bi-Rich Nanostructures

“…In addition to ESI-MS experiments of redissolved single crystals, we performed ESI-MS studies of extraction solutions of "K 5 Ga 2 Bi 4 " in en/crypt-222 (Figures S12−S19; Table S7) and of solutions in which reactions between "K 5 Ga 2 Bi 4 " in en/ crypt-222 and [LaCp S18−S20) indicated different initial species to form under the slightly varied reaction conditions. The major findings of this study and previous investigations 25,[31][32][33][34][35]52 are summarized in Scheme 4.…”

“…In contrast to the well-known tendency of bismuth to form polycations, it was shown only recently that Bi atoms are actually capable of forming polyanionic molecular assemblies: homoatomic, or heteroatomic in combination with other (semi)­metal(s). The synthetic access to Bi-rich polyanionic molecules was achieved through reactions of binary Zintl phases comprising homoatomic anions, K 3 Bi 2 or K 5 Bi 4 , or by employing [K­(crypt-222)] + salts of binary anions, (GaBi 3 ) 2– , (InBi 3 ) 2– , , or (TlBi 3 ) 2– , , in reactions with transition metal, lanthanide, or actinide complexes. − In a significant amount of reactions with the binary anions (GaBi 3 ) 2– and (TlBi 3 ) 2– , the products turned out to comprise Bi atoms as the only main group component, as these anions tend to decompose under release of elemental group 13 metal. This is in contrast to the behavior of pseudo-tetrahedral binary anions of group 14/Bi combinations, in which the heteroatomic bonds usually seem to be strong enough, thus leading to ternary, yet usually less Bi-rich, intermetalloid clusters. − …”

Transition metal complexes of the naked pnictide elements

“…The compound [Bi12Ni7(CO)4] 4is derived from the smaller clusters in this series by thermal de-ligation and oxidation. 160 The anion can be described as having a icosahedral, nickel-centered Bi6Ni6 core. Fused onto this core are two Bi3 triangles that are bonded to Ni atoms on opposing sides of the icosahedron.…”

Cyclic Tribismuthide as a Piano Stool Complex Ligand – Synthesis and Crystal Structure of (η3‐Bi3)M(CO)33– (M = Cr, Mo)

“…Compounds, which contain the heavier homologous Sb 3 ligand can be found only sparsely in the literature ([Mo(CO) 2 (η 5 ‐C 5 H 5 )(η 3 ‐Sb 3 )], [Mo(CO) 2 (η 5 ‐C 5 Me 5 )(η 3 ‐Sb 3 )]), and no example for a Bi 3 piano stool complex has been reported up to now. However, there are heteroatomic deltahedral and intermetalloid bismuth clusters as well as compounds with a CO 2 ‐like linear [Bi–Zn–Bi] 4– [23] or an ozon‐like bent Bi 3 chain [Bi 3 M 2 (CO) 6 ] 3– ( M = Cr, Mo) . For the synthesis of the latter Sevov et al employed K 5 Bi 4 and [(C 9 H 12 )Cr(CO) 3 ] or [(C 7 H 8 )Mo(CO) 3 ] as starting materials in ethylenediamine.…”