Reactive Solubilization of Heterometallic Clusters by Treatment of (TrBi3)2− Anions (Tr=Ga, In, Tl) with [Mn{N(SiMe3)2}2]

Abstract Lowering the charge of Zintl anions by (element‐)organic substituents allows their use as sources of (semi)metal nanostructures in common organic solvents, as realized for group 15 anions or Ge9 4− and Sn9 4−. We developed a new strategy for other anions, using low‐coordinate 3d metal complexes as electrophiles. [K(crypt‐222)]+ salts of (TrBi3)2− anions dissolved in situ in Et2O and/or THF when reacted with [Mn(hmds)2]. Work‐up afforded soluble [K(crypt‐222)]+ salts of [{(hmds)2Mn}2(TlBi3)]2− (in 1), [{(hmds)2Mn}2(Bi2)]2− (in 2), and [{(hmds)Mn}4(Bi2)2]2− (in 3) (crypt‐222=4,7,13,16,21,24‐hexaoxa‐1,10‐diazabicyclo[8.8.8]hexacosane; Tr=Ga, In, Tl; hmds=N(SiMe3)2), representing rare cases of Zintl clusters with open‐shell metal atoms. 1 comprises the first coordination compound of the (TlBi3)2− anion, 2 features a diamond‐shaped {Pn2M2} unit, and 3 is a mixed‐valent MnI/MnII compound. The uncommon electronic structures in 1–3 and magnetic coupling were studied by comprehensive DFT calculations.


Crystal Measurement and Refinement Details
The data sets were collected on a Bruker D8 Quest with microfocus source emitting MoKα radiation (λ = 0.71073Å) and a Photon 100 detector at T = 100 K. The structures were solved by dual space methods of SHELXT-2018/2 within the Olex2-1.3 software [4][5][6] and refined using least-squares procedures on a F 2 with SHELXL-2018/3 in Olex2. [6,7,4] General crystallographic data are listed in Table S1. were drawn with DIAMOND. [8] They are shown with displacement ellipsoids at the 50% probability level for non-hydrogen atoms. Hydrogen atoms are not shown for clarity.   Figure S2. The disorder cannot be reasonably modeled by considering a larger unit cell or a lower symmetry space group; structure solution and refinement in P1 led to the same finding.

Micro-X-Ray Fluorescence Spectroscopy (µ-XFS)
All µ-XFS measurements were performed on a Bruker M4 Tornado, equipped with an Rh-target X-ray tube and a silicon drift detector. Quantification of the elements is achieved through deconvolution of the spectra. The results are summarized in Table S2. The rhodium content from the target is omitted from the quantification results. Figures S5-S7 show the spectra for single crystals of compounds 1·1.5Et2O, 2·4THF, and 3, respectively, along with the results of the deconvolution algorithm. Silicon and potassium contents are notoriously difficult to detect in correct amounts by means of µ-XFS, for which the values are not given here.

Methods
Density functional calculations have been performed using the program Turbomole (Version 7.5.) with the functional TPSSh. [9] The basis set def2-TZVP [10] has been used with the corresponding auxiliary bases and effective core potentials (ECP-60) for thallium and bismuth as well as an ECP-28 for indium. [11] Counter ions have been modeled with the conductor-like screening model (COSMO) [12] using standard settings and an infinite dielectric constant. Force constants and vibrational spectra were calculated using the aoforce program. The absence of any imaginary frequencies proves the structure to be a local minimum. Population analyses were performed using the method of Mulliken, [14] bond orders were calculated using the method of Mayer and Wiberg, [15] and molecular orbitals were plotted with Chemcraft (Version 1.8).
[16] Figure 2 in the main document.

Table S5: Comparison of experimental and calculated interatomic distances (in Å) of the cluster anion in 3.
Atom numbers refer to the ones used in Figure 4 in the main document.

Considerations on the Different Reaction Behavior of (GaBi 3 ) 2-, (InBi 3 ) 2-, and (TlBi 3 ) 2-
We used quantum chemical calculations to explore possible reasons why the three binary anions behave so differently in the syntheses explored in this work.
As an attempt to explore why 1 is observed for Tr = Tl, while starting materials with Tr = In or Ga afford the anion in 2, we calculated the energies for a reaction affording the anion in 2 from that in 1 (and their hypothetical homologues), as shown in equation (1) numbers for the calculated reaction energies. In summary these studies mainly demonstrate the subtle differences between the compounds of the three triel elements, and also indicate the necessity to account for solid precipitates or crystallization in order to explain the experimental findings.

S11
The formation of the anion in 2 was also studied in comparison with the other elemental combinations according to equation (2) Under consideration of the cohesive energies of Tr, as done for equation (1), reaction energies are +2.5, -34.7, or -35.5 kJ/mol (Tr = Ga, In, Tl). Thus, the preference of this structure for Ga and In relative to Tl is obvious and in agreement with the experimental observations -even without consideration of lattice energies in this case, which are likely to enhance the trend for the reasons given above (and the assumption of a relatively stable salt of the highly symmetric (TrBi3) 2anion). S12

Attempts to Measure the Magnetic Behavior of Compound 2
The magnetization measurements were performed on a Quantum Design MPMS-XL SQUID magnetometer operating between 1. 8