The distinction between valence electrons and essentially inactive core electrons is the basis of many classifying concepts in chemistry. However, it has recently been recognized that this is an oversimplification and should, at least in some areas of chemistry, be modified. Many cases are known where cations with closed d10 configurations are subject to homoatomic interactions that influence structure and properties. A characteristic and surprisingly uniform structural feature (e.g., of a number of compounds containing monovalent coinage metals) is a clusterlike assembly of d10 cations that corresponds in geometry and bond lengths to fragments of the metal structures themselves. Further evidence for a special type of bonding in such compounds is provided by their physical properties; for example, the absorption in the UV/VIS region shows a drastic redshift and the compounds are often conductors or semiconductors. The d electrons in such cases have obviously lost their pure “core” nature. All bonding models so far proposed for such systems involve mixing of higher orbitals.

Homoatomic d10–d10 Interactions: Their Effects on Structure and Chemical and Physical Properties

Homoatomare d10‐d10‐Wechselwirkungen — Auswirkungen auf Struktur‐ und Stoffeigenschaften

Small inorganic rings in the 21st century: from fleeting intermediates to novel isolable entities.

Organometallic oxides of main group and transition elements downsizing inorganic solids to small molecular fragments.

Organometallic compounds with SbSb or BiBi bonds

Abstract The reactions of di-tert-butylantimony chloride with sodium hydroxide or sodium sulfide yield new anhydrides or thioanhydrides of tert-butylstibinous acids, which have structures with bridging oxygen or sulfur atoms. Analogous reactions of tert-butylantimonydichloride produce the first examples of anhydrides or thioanhydrides of tertbutylstibonous acids, which have cyclic structures (t-BuSbE)n E = O, n = 3, 4; E = S, n = 2, 3, 4, 5. Structural evidence is based on IR, 1H NMR and MS data.

Anhydride und Thioanhydride von tert-Butylstibinig-und -stibonigsäuren / Anhydrides and Thioanhydrides of tert-Butylstibinous-and Stibonous Acids

Element-element bonds. i. syntheses and structure of tetra-tert-butyltetrarsetane and of tetra-tert-butyltetrastibetane

Synthese und Struktur des Tetra(tert-buty1)tetrarsetans und des Tetra(tert-butyl) tetrastibetans

Dilithium-(tert-butyl)arsenid reagiert mit (tert-Butyl)dichlorarsan zum Tetra(tert-butyl)tetrarsetan 1; das homologe Tetrastibetan 2 bildet sich bei der Reduktion von (tert-Butyl)dichlorstiban mit Magnesium. Die isotypen Verbindungen kristallisieren monoklin in der Raumgruppe P21/c mit Z = 4. Die bei der Mestemperatur von −45 ± 5°C bestimmten Gitterkonstanten von 1/2 sind: a = 957,4(8)/1 000,2(3); b = 1 399,1(14)/1 423,9(4); c = 1 697,4(9)/1 749,8(7) pm; β = 96,02(6)/96,77(3)°. Nach den Ergebnissen der Rontgenstrukturanalysen (3 531/3 232 symmetrieunabhangige Reflexe, Rg = 4,0/4,6%) sind die E4-Ringe (E = As, Sb) gefaltet; die voluminosen organischen Substituenten stehen pseudo-aquatorial in der all-trans-Konfiguration. Charakteristische mittlere Bindungslangen und -winkel sind: EE 244/282; EC 202/221 pm; ∢ EEE 86/85° ∢ EEC 101/99°. Die Diederwinkel der von den Ringatomen aufgespannten Bisphenoide betragen 139/133°.



Element-Element Bonds. I. Syntheses and Structure of Tetra(tert-butyl)tetrarsetane and of Tetra(tert-butyl)tetrastibetane



Dilithium (tert-butyl)arsenide reacts with (tert-butyl)dichloroarsine to give tetra-(tert-butyl)tetrarsetane 1; homologous tetra(tert-butyl)tetrastibetane 2 is formed by reduction of (tert-butyl)dichlorostibane with magnesium. The isotypic compounds 1/2 crystallize in the monoclinic space group P21/c with Z = 4. The dimensions of the unit cells determined at −45 ± 5°C are: a = 957.4(8)/1 000.2(3); b = 1 399.1(14)/1 423.9(4); c = 1 697.4(9)/1 749.8(7) pm; β = 96.02(6)/96.77(3)°. As shown by low temperature X-ray structure determinations (3 531/3 232 symmetry independent reflections; Rg = 4.0/4.6%) the four membered rings E4 (E = As or Sb) are folded; in all-trans configuration the bulky organic substituents occupy pseudo-equatorial positions. Characteristic averaged bond distances and angles are: EE 244/282; EC 202/221 pm; ∢ EEE 86/85° ∢ EEC 101/99°. The dihedral angels of the bisphenoides built up by the atoms of the rings are found to be 139/133°.

Element‐Element‐Bindungen. I. Synthese und Struktur des Tetra(tert‐butyl)tetrarsetans und des Tetra(tert‐butyl)tetrastibetans

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Anhydride und Thioanhydride von tert-Butylstibinig-und -stibonigsäuren / Anhydrides and Thioanhydrides of tert-Butylstibinous-and Stibonous Acids

Element-element bonds. i. syntheses and structure of tetra-tert-butyltetrarsetane and of tetra-tert-butyltetrastibetane

Synthese und Struktur des Tetra(tert-buty1)tetrarsetans und des Tetra(tert-butyl) tetrastibetans

Element‐Element‐Bindungen. I. Synthese und Struktur des Tetra(tert‐butyl)tetrarsetans und des Tetra(tert‐butyl)tetrastibetans