| Identifier | 1 |
|---|---|
| Single-crystal X-ray diffraction, CCDC deposition number | 1579583 |
| Single-crystal X-ray diffraction, rotational disorder of the anion | 15 % Ge occupancy at the P1 position and 5 % P occupancy at each of the Ge2–Ge4 positions |
| Single-crystal X-ray diffraction, anion bond lengths | All bonds are above 2.3 Å; experimental average bond length 2.480 Å |
| NMR reporting reference | Tetramethylsilane (δ ¹H = 0 ppm) and phosphoric acid (85 %, δ ³¹P = 0 ppm) |
| ¹H NMR (300 MHz, DMF-d₇, room temperature) | δ −10.03 (d); the source reports ²J(¹H, ³¹P) as 3.8 Hz in prose and 3.9 Hz in its experimental data |
| ³¹P NMR (DMF-d₇, room temperature) | δ −432.9 |
| ³¹P/¹H-HMQC (DMF-d₇, room temperature) | The ¹H NMR signal at −10.03 ppm correlated with the ³¹P NMR signal at −432.9 ppm; the source states that this is in agreement with a monoprotonated species |
| ESI(−)-MS (fresh solutions in DMF or en) | ‘(Ge₃P)⁻’ (unprotonated, partially oxidized; strongest signal in fresh en solution): m/z 248.7406; (GeP₃)⁻ (low abundance): m/z 166.8430; (HGe₂P₂)⁻ (low abundance; only protonated species identified): m/z 208.7992; ‘(Ge₇P₂)⁻’ (partially oxidized; small amounts): m/z 569.4033; (Ge₇P₂KC₁₈H₃₆O₆N₂)⁻ (small amounts): m/z 984.6232 |
| ESI(−)-MS reporting qualifier | For species not obtained in condensed phase, the source states that generation under ESI-MS conditions cannot be excluded |
Nils Spang, Katrin Beuthert, Tamina Z. Kirsch, Lukas Guggolz, Yannick J. Franzke, Stefanie Dehnen. “From ‘KGeP’ to the protonated P₄-like anion (HGe₃P)²⁻ and the endohedral Zintl cluster [Mn@Ge₁₀P₂]³⁻.” ChemRxiv (). https://doi.org/10.26434/chemrxiv.10002006/v3
The main paper refers to supporting information, but no separate supporting information file was found among the files available from the ChemRxiv record and no working supporting-information link was found on the ChemRxiv article page or in the main paper
| ³¹P NMR (after 22 h) | A signal appears at ≈0 ppm; the source states that this could be a hint for formation of [Mn@Ge₁₀P₂]³⁻ and elsewhere reports binary anions and four- or nine-atom cages in the spectrum |
|---|
| Identifier | 2 |
|---|---|
| Single-crystal X-ray diffraction, CCDC deposition number | 2477793 |
| Single-crystal X-ray diffraction, cage structure and orientation disorder | Non-deltahedral 12-vertex cage with an interstitial Mn atom; threefold orientation disorder with site occupancy factors of 43.7 %, 21.8 %, and 34.5 %, including statistical 10:2 disorder of Ge and P atoms on all sites |
| Single-crystal X-ray diffraction, Mn···Ge/P distances across the three disordered cages | 2.473(17)–2.806(18) Å; average 2.660 Å across 36 distances |
| Single-crystal X-ray diffraction, Ge–Ge/P bond lengths across the three disordered cages | 2.369(6)–2.670(7) Å; average 2.469 Å across 18 bonds |
| Single-crystal X-ray diffraction, distances between cage atoms and centroids of opposite faces | Smallest 4.009 Å; largest 4.775 Å |
| µ-XFS, atomic ratio | K₄.₀₅Mn₁.₄₁Ge₁₀.₀₀P₁.₈₆; the source reports a typical method error below ±1 atom |
| In situ ESI(−)-MS | m/z 842.1022, which the source states can be assigned to [Mn@Ge₁₀P₂]⁻ |
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