Ionothermal Syntheses, Crystal Structures, and Chemical Bonding of the Rhodium‐Centered Clusters [RhBi₉]⁴⁺and [(RhBi₇)I₈]

Abstract

Abstract. The first filled Bi 9 5+ polycation was isolated in the form of [RhBi 9 ](AlCl 4 ) 4 crystals by dissolution of the solid precursor Bi 12-x RhX 13-x in the Lewis-acidic ionic liquid [BMIm]Cl·3.6AlCl 3 (BMIm = 1-butyl-3-methylimidazolium) at 140°C. In the monoclinic crystal structure [P2 1 /n, a = 1217.5(2) pm, b = 1741.6(3) pm, c = 5085.7(7) pm, β = 90.117 (8)

The Intermetalloid Clusters [Ni2Bi12]4+and [Rh2Bi12]4+– Ionothermal Synthesis, Crystal Structures, and Chemical Bonding

“…The DI values (Table S4, Supporting Information) lie in a range typical for Bi–Bi and Bi–Rh bonds as found, for example, in the intermetalloid [RhBi 9 ] 5+ cluster with strong covalent bonding . The computed δ (Rh, Bi) values are higher than the corresponding δ (Ni, Bi) ones, which goes in line with the intensification of the pairwise interaction at the cost of the multicenter one, as discussed above.…”

“…Therefore, we assume that at least a pre‐reacted rhodium‐containing species is required for the formation of [Rh 2 Bi 12 ][AlBr 4 ] 4 at the chosen temperature. Syntheses in the chloride‐based IL [BMIm]Cl · n AlCl 3 yielded [RhBi 9 ][AlCl 4 ] 4 …”

“…Establishing ionic liquids (ILs) as reaction media for the (ionothermal) synthesis of inorganic materials has not only allowed their resource‐efficient production, but also lead to the discovery of new compounds . Among the latter are various new bismuth‐transition metal clusters, [RhBi 9 ] 4+ , [ M Bi 10 ] 4+ ( M = Pt, Pd), [Au(Bi 8 ) 2 ] 5+ , [CuBi 8 ] 3+ , and [(RhBi 7 )Br 8 ] (Figure ) , . These intriguing entities model the transition from conventional coordination compounds to intermetalloid clusters and thereby challenge the limits of chemical bonding concepts, such as counting rules for complexes or Wade‐Mingos clusters.…”

[Co@Sn6Sb6]3−: An Off‐Center Endohedral 12‐Vertex Cluster

“…A total cluster charge of −3 appears to be favored owing to the requirements of crystallization with [K(crypt‐222)] + cations. Anions 2 and 3 are isoelectronic and isostructural with both each other and the aforementioned Bi‐containing clusters, [Ni 2 @E 7 Bi 5 ] 3− (E=Sn, Pb), as well as a related polycation, [Ni 2 @Bi 12 ] 4+ . Anion 1 , however, possesses the same basic fused square‐antiprism structure, yet notably with only one 8‐atom “pocket” occupied.…”

The Subbromide Bi5Br4 – On the Existence of a Hidden Phase

“…It took five more decades to explore the binary phase diagrams and to develop the chemistry of bismuth‐rich compounds. Today, the polyhedral polycations Bi 5 + ,, Bi 5 3+ , Bi 6 2+ ,, Bi 8 2+ , Bi 9 5+ ,, and Bi 10 4+[23–38] are known, either as homoatomic entities or as parts of bismuth‐rich intermetalloid clusters additionally including electron‐rich transition metal atoms. This provided the basis for a detailed understanding of the structural and bonding principles in such clusters …”