OR or OOR? The oxygenation of ZntBu2 in the presence of donor ligands demonstrates the tendency of zinc dialkyls to undergo oxidation of only one ZnC bond under controlled conditions (see scheme). The formation of alkoxide or peroxide species is influenced by the type of donor ligand employed, and these divergent pathways offer a glimpse into the general mechanism of dioxygen activation.

Structural studies of the homoleptic main group metal alkyls are of fundamental interest to rationalize their physical behavior and reactivity, and they provide novel supramolecular structures with remarkable topologies and often unusual metal-ligand interactions. For instance, the structure of heavier group 13 trimethyls is topologically equivalent to the well-known zeolite type structures, 1 and the structure characterization of Mg t Bu 2 (i.e., the simplest dialkylmagnesium compound to be structurally authenticated) revealed that intra-and intermolecular CH 3 ‚‚‚Mg agostic interactions play a substantial role in the molecular assembly. 2 As noted by Seyferth in the seminal paper on the history of zinc alkyls chemistry, in recent years, there has been a renaissance in dialkylzinc chemistry due to the utility of this family of compounds in important synthetic processes. 3 Up to now, however, the structurally authenticated homoleptic dialkylzincs consist of sterically strongly encumbered methylsilyl ligands, 4 though some of lower zinc alkyls were investigated by a host of techniques 5 including molecular weight determination, NMR and IR spectroscopy, gas electron diffraction, and photoelectron spectroscopy. 6 Other structurally known examples are restricted to a very recently reported divinylzinc compound 7 and some diarylzinc compounds, including the unique structure of diphenylzinc, in which the monomeric ZnPh 2 units are associated into unsymmetrical dimers that are linked by further weaker interactions into tetrameric units. 8 Moreover, systematic investigations on the structure and relative stability of the ZnR 2 (L) n adduct as a function of the character of both the R substituent and L ligand are also relatively sparse. For instance, to our knowledge, of the Lewis acid-base adducts involving Zn t Bu 2 , only the threecoordinate ZnR 2 (L) complexes with the iminato ligand have been structurally authenticated. 9,10 On the other hand, during the past decade, the controlled selfassembly of metal-ligand complexes has attracted great attention owing to their wide potential applications as functional materials, and many supramolecular compounds with intriguing structures have been synthesized and characterized, such as the 1D chains, 2D layers, and 3D open frameworks. 11 In regard to 2D metalorganic frameworks, where honeycomb, brick wall, grid, square, or rectangular networks are known, nanofabrics still await their realization (Chart 1). 12 We report here a system involving Zn t Bu 2 and bipyridine ligands that brings together the major features mentioned above: the molecular structure of homoleptic metal alkyl and self-assembly of a metal-ligand complex leading to unprecedented topology of the 2D framework based on coordination polymers sustained by organometallic nodes.The limited experimental structural data for tert-butylzinc derivatives stimulated our interest in Zn t Bu 2 (1) and its adducts with pyridine ligands. The homoleptic starting compound 1 was prepared in high yield according to the literature ...

We report on investigations of reactions of tBu(2)Zn with 8-hydroxyquinoline (q-H) and the influence of water on the composition and structure of the final product. A new synthetic approach to photoluminescent zinc complexes with quinolinate ligands was developed that allowed the isolation of a series of structurally diverse and novel alkylzinc 8-hydroxyquinolate complexes: the trinuclear alkylzinc aggregate [tBuZn(q)](3) (1(3)), the pentanuclear oxo cluster [(tBu)(3)Zn(5)(μ(4) -O)(q)(5)] (2), and the tetranuclear hydroxo cluster [Zn(q)(2)](2)[tBuZn(OH)](2) (3). All compounds were characterized in solution by (1)H NMR, IR, UV/Vis, and photoluminescence (PL) spectroscopy, and in the solid state by X-ray diffraction, TGA, and PL studies. Density functional theory calculations were also carried out for these new Zn(II) complexes to rationalize their luminescence behavior. A detailed analysis of the supramolecular structures of 2 and 3 shows that the unique shape of the corresponding single molecules leads to the formation of extended 3D networks with 1D open channels. Varying the stoichiometry, shape, and supramolecular structure of the resulting complexes leads to changes in their spectroscopic properties. The close-packed crystal structure of 1(3) shows a redshifted emission maximum in comparison to the porous crystal structure of 2 and the THF-solvated structure of 3.

Zinc links: Solid‐state desolvation of the dimeric alkoxide [{tBuZn(μ‐OtBu)(thf)}2] leads to a trimer [{tBuZnOtBu}3] with a unique core structure; subsequent grinding affords the tetrameric cubane [{tBuZnOtBu}4]. This approach demonstrates a new direction in the generation of metal alkoxide clusters.

The first magnesium and zinc alkyls derived from N-(iso-propyl)-pyrrolylaldimine have been synthesised and structurally characterised: both tBuM(N,N')-type compounds exist as three-coordinate monomers in benzene solution, but in the solid state the magnesium complex is a centrosymmetric dimer with Mg2(mu-N)2 bridges, whereas the zinc complex is a Zn...pi bonded dimer with a pi-coordinated pyrrole unit.

OR oder OOR? Am Beispiel der Oxygenierung von ZntBu2 in Gegenwart von Donorliganden zeigt sich die Neigung von Dialkylzink zur Oxidation nur einer Zn‐C‐Bindung unter bestimmten Bedingungen (siehe Schema). Ob dabei Alkoxid‐ oder Peroxid‐Spezies entstehen, hängt vom eingesetzten Donorliganden ab. Diese divergenten Reaktionswege geben Einblick in den allgemeinen Mechanismus der Disauerstoff‐Aktivierung.

Schritt für Schritt zum Cluster: Die Festkörperdesolvatisierung des dimeren Alkoxids [{tBuZn(μ‐OtBu)(thf)}2] führt zum trimeren [{tBuZnOtBu}3] mit einzigartiger Kernstruktur. Anschließendes Zermahlen ergibt das tetramere Cuban [{tBuZnOtBu}4]. Dieses Ergebnis zeigt einen neuen Ansatz für die Herstellung von Metallalkoxidclustern auf.