[(η³-Bi₃)₂(IrCO)₆(μ₄-Bi)₃]³⁻: a new archetype of a 15-vertex deltahedral hybrid from Bi_x^x−-coordination aggregation of cationic [IrCO]⁺ units

Abstract

The first Zintl-deltahedral metal carbonyl hybrid [(η3-Bi3)2(IrCO)6(μ4-Bi)3]3− was obtained by a new synthetic methodology, namely the Bixx−-coordination aggregation of [Ir(CO)]+ to trigonal prismatic [Ir(CO)]66+.

Aggregation of Polybismuthide Anions in a Single Compound Using +Rh-CO Units: Heterometallic Cluster Ions [Rh@Bi10(RhCO)6]3– and [Rh@Bi9(RhCO)5]3–

“…The synthesis procedures causing this difference lie in the source of the + Rh-CO units [i.e., Rh 2 (CO) 4 Cl 2 for 1 and Rh­(acac)­(CO) 2 for 2 ] and the reaction temperature (i.e., the room temperature for 1 and 60 °C for 2 ). The present work, together with the study on [(η 3 -Bi 3 ) 2 (IrCO) 6 (μ 4 -Bi) 3 ] 3– , clearly demonstrates that various kinds of polybismuthide anions can be aggregated together into individual heterometallic cluster ions by using + M-CO (M = Ir, Rh) units, depending on the source of + M-CO (M = Ir, Rh) units and reaction conditions. Our DFT calculaions suggest a significant amount of electron transfer from the polybismuthide anions to the + Rh-CO groups in 1 and 2 .…”

“…The latter in turn would promote the breaking of the Rh–Cl or the chelating Rh-acac bonds at a lower temperature. Another example is [(η 3 -Bi 3 ) 2 (IrCO) 6 (μ 4 -Bi) 3 ] 3– , prepared by reacting the en solution of K 5 Bi 4 with Ir­(acac)­(CO) 2 at room temperature, which leads to the [K­(2,2,2-crypt)] + salt.…”

“…3.4008(9) Å) found in [Bi 7 (RhCO) 3 ] 2– , but they are longer than those found in [(η 3 -Bi 3 ) 2 (IrCO) 6 (μ 4 -Bi) 3 ] 3– ( av. 3.087 (2) Å) and (η 3 -Bi 3 )­M­(CO) 3 3– (M = Cr, Mo) ( av. 2.98 Å) .…”

“…22 However, it is still rare to find large Bi-M (M = Ni, Zn) heterometallic clusters prepared by reactions of homoatomic polybismuthides with transition-metal complexes. Very recently, our group reported a new type of heterometallic cluster, [(η 3 -Bi 3 ) 2 (IrCO) 6 (μ 4 -Bi 3 ) 3 ] 3− , 23 from the aggregation of polybismuthide anions with + Ir-CO fragments. From the viewpoint of the local bonding environment around each Ir + cation, this 15-vertex deltahedral cluster can be described as being composed of six Bi 4 Ir-CO square pyramids with the CO ligands at the apical positions.…”

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

“…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. − …”