[Ga₁₆(PtBu₂)₁₀]: ein mit Galliumphosphid ummantelter Kern aus vier nackten Ga‐Atomen?

Discussion on the Formation and Bonding in Three [Ga8R10] Compounds: The Diversity in Classical GaGa Bonds

“…8 Cl 2 ] (6): When the metastable GaCl solution described in the synthesis of 5 was treated with a small excess of LiPtBu 2 suspended in toluene, a dark-colored pentane extract was finally obtained following the thermal treatment described in the Experimental Section. In this fraction red crystals of 6 were formed as a by-product of the metalloid cluster [Ga 16 A C H T U N G T R E N N U N G (PtBu 2 ) 10 ] [12] described previously. The result of the structural analysis of this compound and selected bonding parameters are presented in Figure 1b.…”

[Ga51(PtBu2)14Br6]3−: An Elementoid Gallium Cluster with Metalloid and Nonmetalloid Structural Elements

“…[4] Given these results, we asked ourselves if it would be possible to synthesize larger Ga n cores in metalloid clusters with surrounding GaPR 2 shells by choosing the right conditions. In this case, we would expect centered structures with high coordination numbers for the central gallium atom, as in the fcc packing that was recently found in Ga-IV at high pressures.…”

“…To vary the influence of the outer shell, we recently introduced PtBu 2 groups. [4] Steric and electronic influences cause the phosphorus atoms in these groups to form also bridging bonds, which result in their increased interaction with the Ga n core (Scheme 1 b).…”

“…The roughly 2 nm clusters are in a slightly distorted cubic closepacked arrangement, in which all of the tetrahedral holes are filled with [Li(THF) 4 ]…”

“…A metastable solution of GaBr in toluene/THF (3:1) was heated from À78 to À35 8C, [1,6] to induce the disproportionation to form metal-rich clusters and GaBr 3 . Subsequently, a slight excess of LiPtBu 2 suspended in toluene was added, and the reaction mixture was heated to 60 8C for 2 h. After several days in a drying oven at about 50 8C, compound 1 crystallizes as black rhombuses, which contain one [Li 2 Br(THF) 6 ] + and two [Li(THF) 4 ]…”