Au₁₀₈S₂₄(PPh₃)₁₆: A Highly Symmetric Nanoscale Gold Cluster Confirms the General Concept of Metalloid Clusters

Abstract

The reduction of (Ph P)AuCl with NaBH in the presence of HSC(SiMe ) , leads to one of the largest metalloid gold clusters: Au S (PPh ) (1). Within 1 an octahedral Au core of gold atoms arranged as in Au metal is surrounded by 48 oxidized Au atoms of an Au S shell, a novel building block in gold chemistry. The protecting Au S shell is completed by additional 16 Au(PPh ) units, leading to a complete protection of the gold core. Within 1 the Au-Au distances get more molecular on going from the center to the ligand shell. Cluster 1 represents novel structural motives in the field of metalloid gold clusters which also are partly typical for metal atoms in metalloid clusters: M R (n>m).

Reactions of GeCl2 with the Thiolate LiSC(SiMe3)3: From thf Activation to Insertion of GeCl2 Molecules into C−S Bonds

“…This shows that LiSTsi not only acts as a source of the substituent but also as a donor of sulfur atoms and oxidant of the germanium atoms. This ability of LiSTsi was also recently observed during the synthesis of the giant metalloid gold clusters Au 108 S 24 (PPh 3 ) 16 and Au 70 S 20 (PPh 3 ) 12 …”

An Atomically Precise Alkynyl‐Protected PtAg42 Superatom Nanocluster and Its Structural Implications

“…However, our study clearly indicates that the function of SbF 6 − in nanoclusters should be revised since it is not only a counterion but also an alternative protective unit. The SbF 6 − anion in 1 , together with the previously verified H − , X − (X=Cl, Br), S 2− , and BF 4 − ions, offers us strong evidence that simple inorganic anions do not only balance charge.…”

Synthesis and Characterization of Gold Silyl Compounds with Different Phosphine or Phosphite Groups for Reduction Reactions

“…The chemical shifts are given in ppm against external standards SiMe 4 ( 1 H, 13 C, 29 Si) and 85 % phosphoric acid ( 31 P). Toluene, Et 2 O and THF were dried with sodium and pentane was dried with CaH 2 .…”

“…Toluene, Et 2 O and THF were dried with sodium and pentane was dried with CaH 2 . HSC(SiMe 3 ) 3 , [13] (THT)AuCl, [20] (THF) LiSSi(SiMe 3 ) 3 , [21] Ph 3 PAuCl, [26] Et 3 P and nPr 3 P [27] were synthesized as described in the literature. The obtained solids were stored in a glovebox under argon atmosphere.…”

“…mmol) was dissolved in Et 2 O (20 mL) and decanted to (MeO)3 PAuCl. The remaining solid was dissolved in pentane (10 mL) and the pale-yellow solution was stored at -28°C leading to colorless blocks of (MeO) d, J = 14 Hz, 9 H, OMe), 0.55 (s, 27 H, SiMe 3 ) ppm 13. The Et 2 O was removed and the remaining grey solid was dissolved in Et 2 O (30 mL).…”