[Ge₄O₆Te₄]^4—, an Adamantanoid Oxotellurido Germanate(IV) with a Central Ge₄O₆ Core

Abstract

Mn(en) 3 ] 2 [Ge 4 O 6 Te 4 ]·1.5en (1) and (enH) 3 [Mn(en) 3 ] 3 -[Ge 4 O 6 Te 4 ] 2 I·4.7en (2) may be prepared at 150°C by solvothermal reaction of elemental Ge and Te with Mn(OOCCH 3 ) 2 ·4H 2 O in the presence of [CH 3 ) 4 N]I as a mineralizer in respectively superheated ethylenediamine (en) or an en/CH 3 OH (3:2) mixture. Both contain the novel [Ge 4 O 6 Te 4 ] 4Ϫ anion with a central adamantanoid Ge 4 O 6 core and four terminal Te atoms and represent the first examples

Synthesis and Structures of Dimanganese(II) Complexes with Spirotricyclic [Mn(μ‐Ge2Se7)Mn] and [Mn(μ‐Sn2Se6)Mn] Cores

“…As for the spirotricyclic Sn IV compound, the Mn-Se t distances of 2.725(2)Ϫ2.745(2) Å in 1 are, once again, much longer than those of 2.55Ϫ2.60 Å typically observed for non-cyclic Mn-Se bonds. Interestingly, the Ge-Se t bond lengths of 2.298(1)Ϫ2.314(2) Å in this complex are similar to those of 2.298(2)Ϫ2.320(2) Å found in the discrete [Ge 2 Se 7 ] 4Ϫ anions of (enH 2 )[{Mn(en) 2 (enH)} 2 (μ-en)][Ge 2 Se 7 ] 2 [19]. Both the weakness of the Mn-Se t bonds and the closeness of the Se t -Ge-Se t Ј angles [108.02(5) and 107.38(5)°] to the ideal tetrahedral value may contribute to the relative strength of the Ge-Se t bonds in 1.…”

Two Novel Adamantane‐Like Thio/Selenidogermanates with Complex Cations

“…Notably, only [Ge 2 Q 6 ] 4– (Q = S, Se), [Ge 2 Se 7 ] 4– , and [Ge 5 Te 10 4– ] n anions combined with metal complexes were observed, but [Ge 4 Q 10 ] 4– anions have not been characterized in the presence of such complexes. An exception are oxotellurido germinates [Mn(en) 3 ] 2 [Ge 4 O 6 Te 4 ]·1.5en12 and (enH) 3 [Mn(en) 3 ] 3 ‐[Ge 4 O 6 Te 4 ] 2 I·4.7en,12 where terminal oxygen atoms of Ge 4 O 10 are replaced by four tellurium atoms. Herein, we present two new thio/selenidogermanates [Ni 2 (μ‐teta)(teta) 2 ]Ge 4 S 10 ·H 2 O ( 1 ) and [Ni(teta) 2 ] 2 Ge 4 Se 10 ·0.5H 2 O ( 2 ) (teta = triethylenete‐tramine).…”

All-metallagermoxane with an adamantanoid cage structure: [(Cp*Ru(CO)2Ge)4(μ-O)6] (Cp* = η5-C5Me5)

“…The 1 H NMR spectrum displayed a signal at δ = 1.76 ppm that rationalizes the presence of a single type of Cp* ligand indicating high symmetry. The presence of the Cp* ligand has also been supported by 13 C NMR.…”

“…12 In addition, Sheldrick et al recently reported a germoxane with an adamantanoid structure. 13 The presence of metals on germoxanes has attracted considerable interest after the isolation of a dimetallagermoxane by Cotton and co-workers. 14 The number of compounds known under this category is very few (Chart 1) 15 and to date, only one cyclic trimetallagermoxane is known, reported by Filippou.…”

“…16 As shown in Scheme S1 (ESI †), treatment of [(Cp*RuCO)-(GeCl 2 )] 2 , 1 with 4.2 equivalents of K metal in THF followed by purging the intermediate with oxygen led to the formation of 2. ‡ It was isolated as pale yellow crystals which were characteri-zed by 1 H and 13 C NMR, IR and by single-crystal X-ray crystallography. The mass spectrum of 2 showed a molecular ion peak at m/z 1556.…”