Substantial π-aromaticity in the anionic heavy-metal cluster [Th@Bi12]4−

Abstract

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Tetrahedral [Sb(AuMe)4]3−Occurring in Multimetallic Cluster Syntheses: About the Structure‐Directing Role of Methyl Groups

“…Multimetallic compounds have been in the focus of research groups across the world for av ariety of reasons, ranging from the exploration of their mere accessibility or their structures and bonding,totheir use as precursors to new intermetallic phases or in bond activation processes. [1][2][3][4][5][6][7] An elemental combination that attracted much attention is that of Sb and Au,due to relatively high electron affinities of both metals (Sb:103.2 kJ mol À1 ,A u: 222.8 kJ mol À1 ), thus allowing for different polarization of the bond. [8] One class of respective compounds comprises neutral or cationic complexes with essentially isolated Sb-Auc on-tacts.…”

“…[18] Such ligand-free multimetallic anions belong to the family of Zintl clusters that can be accessed by reacting homo-or heteroatomic p-block metal anions with d-block or f-block metal compounds. [7] In this context, reactions of x [K(crypt-222)] 2 (Sn 2 Sb 2 )•en with y [AuMePPh 3 ]w ere reported to yield [K(crypt-222)] 3 -[(Sn 2 Sb 2 ) 2 Au]( A) [19,20] in en (x:y = 2:1) or [K(crypt-222)] 4 -[(Sn 5 Sb 3 Au) 2 ]•2 py (B) [18] in pyridine (x:y = 1:2) (crypt-222 = 4,7,13,16,21,24-hexaoxa-1,10-diazabicyclo[8.8.8]-hexacosane, en = ethane-1,2-diamine;p y = pyridine), yet the underlying reactions are only poorly understood. Thef ormation of the anion in A,[{(Sn 2 Sb 2 ) 2À } 2 Au + ] 3À ,atfirst glance shows no sign of redox chemistry in comparison with the reactants.H owever,t he anion in B,[ {(Sn 5 Sb 3 ) 3À Au + } 2 ] 4À ,i so verall oxidized relative to the (Sn 2 Sb 2 ) 2À anion-and in both cases,t he gold complex apparently released not only the PPh 3 groups,b ut also the (CH 3 ) À ligands.F or this,i ti sv ery obvious that side reactions take place that have not yet been elucidated.…”

Tetrahedral [Sb(AuMe)4]3−Occurring in Multimetallic Cluster Syntheses: About the Structure‐Directing Role of Methyl Groups

“… Suggestion of reactions to take place at different stoichiometries of (Sn 2 Sb 2 ) 2− and [AuMePPh 3 ], and in different solvents, to form the ternary anions [(Sn 2 Sb 2 ) 2 Au)] 3− (in A , top), [(Sn 5 Sb 3 Au 2 ) 2 ] 4− (in B , center and bottom), or [Sb(AuMe) 4 ] 3− (in 1 , bottom), respectively. Note that all mentioned side‐products were experimentally proven to form (“Sb 3− ” in 1 as soon as enough {AuMe} is available), except for the 4,4′‐bipyridyl radical anion (C 10 H 8 N 2 ) .− and (H 2 NCH 2 CH 2 NH) − ; these anions, however, were mentioned as side‐products of Zintl cluster formation in previous work [7b, 37] …”

Trendbericht Festkörperchemie 2022

“…Rechts: Berechneter Ringstrom in [Th@Bi 12 ] 4mit Plot der magnetisch induzierten Stromdichte (in atomaren Einheiten), wobei das magnetische Feld senkrecht zur molekularen Ebene steht. 19) Abb. 6.…”