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 Ge94− and Sn94−. 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.

Taming Super-Reduced Bi23–Radicals with Rare Earth Cations

“…A particularly intriguing candidate for generating a radical ligand is the heaviest nitrogen homolog bismuth that should engender strong coupling due to its 6s and 6p valence orbitals that have much larger radial extents compared to the 2s and 2p valence orbitals for the existing nitrogen bridges, alongside significant relativistic effects that could enhance magnetic anisotropy. , When it comes to lanthanide chemistry, however, bismuth is a poor donor ligand . A viable synthetic path to render bismuth more accessible in coordination chemistry involves dibismuthane ligands that are formed through reductive coupling of BiR 3 , BiRX 2 , or BiCl 3 , where R = phenyl or 2,6-dimesitylphenyl, − and Zintl anionic ligands. , Such ligands coordinate relatively strongly to metals through their p-orbital valence electrons and give rise to complexes with d-block metals such as Mn, Fe, Co, Mo, W, and Zr. , While dibismuth serving as a π-donor ligand has been described in the realm of transition metals, only one example with a rare earth metal is currently known, but none of them contain a dibismuth radical. The only other rare earth metal complex in which bismuth binds directly to the metal ion is the recently isolated lanthanide–bismuth heterometallocubane cluster from our group containing an unprecedented Bi 6 6– Zintl ion .…”

“…33,34 Such ligands coordinate relatively strongly to metals through their p-orbital valence electrons and give rise to complexes with d-block metals such as Mn, Fe, Co, Mo, W, and Zr. 34,35 While dibismuth serving as a π-donor ligand has been described in the realm of transition metals, 33 only one example with a rare earth metal is currently known, 30 but none of them contain a dibismuth radical. The only other rare earth metal complex in which bismuth binds directly to the metal ion is the recently isolated lanthanide−bismuth heterometallocubane cluster from our group containing an unprecedented Bi 6…”

Synthesis and Characterization of Novel Transition Metal Pnictogenide Compounds.

“…However, a look at the higher homologs of the (N(SiMe 3 ) 2 ) 2 group reveals that only few phosphorus and arsenic species and no antimony or bismuth species of the form [M{E(SiMe 3 ) 2 } 2 ] are known (Figure 2). [15–27] …”

“…However, a look at the higher homologs of the (N(SiMe 3 ) 2 ) 2 group reveals that only few phosphorus and arsenic species and no antimony or bismuth species of the form [M{E(SiMe 3 ) 2 } 2 ] are known (Figure 2). [15][16][17][18][19][20][21][22][23][24][25][26][27] Also known are transition metal compounds with one NacNac ligand and one N(SiMe 3 ) 2 substituent, see Figure 2. [15][16][17][28][29][30][31][32][33][34] This also shows that no analogous species of formula [(Dipp 2 NacNac)ME(SiMe 3 ) 2 ] (M = 3d-metal, E = P, As, Sb, Bi) are described to date.…”