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Investigating the interactions of f-block metal ions with p-block polyanions in multinary cluster compounds is becoming increasingly attractive but remains a challenge in terms of both the synthetic approach and the control of the structures that are formed during the syntheses. So far, two types of reactions were dominant for the formation of corresponding clusters: the reaction of binary anions of p-block elements in 1,2-diamino-ethane ( en ) solutions or the reaction of organobismuth compounds with corresponding f-block metal complexes in THF. Herein, we report the synthesis of [La@In 2 Bi 11 ] 4- ( 1 ) and its doubly μ-Bi-bridged analogue in the doubly [K(crypt-222)] + -coordinated {[K(crypt-222)] 2 [La@In 2 Bi 11 ](μ-Bi) 2 [La@In 2 Bi 11 ]} 4- ( 2 ) as their [K(crypt-222)] + salts [K(crypt-222)] 4 1 and [K(crypt-222)] 4 2 , respectively, achieved by reactions of [InMes 3 ] and [La(C 5 Me 4 H) 3 ] (Mes = mesityl, C 5 Me 4 H = tetramethylcyclopentadienyl) with K 10 Ga 3 Bi 6.65 /crypt-222 (crypt-222 = 4,7,13,16,21,24-hexaoxa-1,10-diazabicyclo[8.8.8]hexacosane) in en . In the absence of [La(C 5 Me 4 H) 3 ], the otherwise unchanged reactions afford the anions [Bi 6 (InMes)(InMes 2 )] 3- ( 3 ) and [Mes 3 In-InMes 3 ] 2- ( 4 ) instead, which can be isolated as their [K(crypt-222)] + salts [K(crypt-222)] 3 3 and [K(crypt-222)] 2 4 ·tol (tol = toluene), respectively. The {Bi 6 } fragment observed in anion 3 is assumed to be one of the key intermediates not only toward the formation of 1 and 2 but also on the way to more general bismuth rich compounds.

The impact of 4f metal ions Ln 3+ (Ln = La or Ce) versus 5f metal ions U n + ( n = 3 or 4) on the compositions and distribution of 5p metal atoms in the cluster shells of endohedral species [M@Sn 14- x Sb x ] q - (M = La, Ce, or U; x = 6-8; q = 3, 4) was studied by means of combined experimental and quantum chemical investigations. While all known f-block metal ion-centered endohedral clusters possessed combinations of larger main group metal atoms so far (Sn/Bi or Pb/Bi), resulting in mixtures of 13- and 14-atom cages, the 14-atom cages reported herein comprise exclusively Sn and Sb atoms and therefore are challenged in accommodating the large 4f and 5f ions. We show that the clusters form in reactions of (Sn 2 Sb 2 ) 2- anions with [Ln(C 5 Me 4 H) 3 ] or [U(C 5 Me 4 H) 3 Cl], and that salts of [La@Sn 6 Sb 8 ] 3- , [La@Sn 7 Sb 7 ] 4- , [U@Sn 8 Sb 6 ] 4- , and [U@Sn 7 Sb 7 ] 3- can be isolated from them. The assignment of Sn versus Sb in the encapsulating cage follows a simple rule. Different central atoms cause only slight differences in this regard and with respect to distortions of the cluster shells. The reactions also yielded the salt of the new binary anion (Sn 4 Sb 4 ) 2- that was recently predicted by quantum chemical studies.