Polyhedral Bismuth Polycations Coordinating Gold(I) with Varied Hapticity in a Homoleptic Heavy‐Metal Cluster

Abstract

Shiny black, air-sensitive crystals of [Au(Bi-8)(2)](AlCl4)(5) were obtained from the reaction of AuCl, BiCl3, and bismuth in the ionic liquid [BMIm] Cl center dot 4AlCl(3) (BMIm = 1-n-butyl-3-methylimidazolium) at 180 degrees C. [Au(Bi-8)(2)](AlCl4)(5) crystallizes in the monoclinic space group P2(1)/n. In the heavy-metal cluster [Au(Bi-8)(2)](5+), two square-antiprismatic Bi-8(2+) polycations coordinate the gold(I) atom in eta(2)-and eta(4)-mode, respectively. Quantum chemical calculations demonstrate that both Bi-8(2+) polycations involve skeletal electrons for the donor bonding, which causes a widening of Bi-Bi distances compared with those in free Bi-8(2+)

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

“…[RhBi 9 ](AlCl 4 ) 4 Black, air-sensitive, flat needles of [RhBi 9 ](AlCl 4 ) 4 with lengths of up to several millimeters crystallized upon dissolution and conversion of the solid ternary precursor Bi 12-x RhX 13-x (X = Cl, Br) [9d] in the Lewis-acidic IL [BMIm]Cl·3.6AlCl 3 (BMIm = 1-n-butyl-3-methylimidazolium) at 140°C. The precursor compounds are cluster salts that consist of Bi 5 + and Bi 6 2+ polycations as well as [(RhBi 6 )X 12 ] -and [(RhBi 6 )X 13 ] 2-(X = Cl, Br) anions (crystal structure in Figure S1, Supporting Information).…”

“…Air-sensitive samples were filled into 0.3 mm to 0.5 mm wide glass capillaries and sealed within a glove box 4 on a fourcircle Bruker CCD diffraction system Kappa APEX2 using graphitemonochromated Mo-K α radiation (λ = 71.073 pm) and for Bi 7 RhI 8 with an imaging plate diffraction system IPDS-II (Stoe). All data sets were corrected for background, polarization, and the Lorentz factor.…”

“…Among them are [Ru(Bi 8 ) 2 ] 6+ , [3] [Au(Bi 8 ) 2 ] 5+ , [4] [Mo 2 Te 12 ] 6+ , [5] and [M 2 Bi 12 ] 4+ (M = Ni, Rh). [6] The latter has an anionic counterpart, [Ni 2 Sn 7 Bi 5 ] 3-, with the same structure and valence-electron count.…”

Low-Temperature Ordering in the Cluster Compound (Bi8)Tl[AlCl4]3

“…The crystal structure of bismuth monochloride (Bi 6 Cl 7 ), reported by Corbett and Hershaft in 1962 [1], was the first example of a solid containing a homonuclear bismuth polycation. Ever since then, a number of compounds have been synthesized, showing bismuth clusters of various sizes and shapes either isolated [1][2][3][4][5][6][7] or coordinating to electron-rich transition metals like Au, Cu, or Ru [8][9][10][11][12][13]. These cationic clusters typically form in bismuth-rich halide melts.…”

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

“…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.…”