Cover Picture: Substituent‐Free Gallium by Hydrogenolysis of Coordinated GaCp*: Synthesis and Structure of Highly Fluxional [Ru2(Ga)(GaCp*)7(H)3] (Angew. Chem. Int. Ed. 21/2009)

Soft skin, hard core …? is the basic principle for the formation of a nano‐alloy from molecular precursors. The co‐hydrogenolysis of ruthenium complexes in presence of GaCp* gives the isolable key intermediate [Ru₂(Ga)(GaCp*)₇(H)₃] featuring a substituent‐free bridging gallium atom. From this “embryonic” species Ru/Ga phases are formed by complete cleavage of the protective Cp* shell (depicted as an eggshell in the Cover picture), as described by R. A. Fischer et al. in their Communication on page 3872 ff.

     

Substituent‐Free Gallium by Hydrogenolysis of Coordinated GaCp*: Synthesis and Structure of Highly Fluxional [Ru2(Ga)(GaCp*)7(H)3]

All change : Complete ligand exchange through the hydrogenation of [Ru(η⁴‐cod)(η⁶‐cot)] in the presence of GaCp* under mild conditions leads to the title complex featuring a “naked” gallium atom bridging two ruthenium centers (see structure: C white, Ga blue, Ru red). This cluster can be considered as a trapped intermediate on the way to mixed‐metal nanoparticles; cot=1,3,5‐cyclooctatriene; cod=1,5‐cyclooctadiene, Cp*=C₅Me₅.

     

Triangular Nickel Complexes Derived from 2‐Pyridylcyanoxime: An Approach to the Magnetic Properties of the [Ni3(μ3‐OH){pyC(R)NO}3]2+ Core

A series of nickel complexes with nuclearity ranging from Ni₃ to Ni₆ have been obtained by treatment of a variety of nickel salts with the 2‐pyridylcyanoxime ligand. The reported compounds have as a common structural feature the triangular arrangement of nickel cations bridged by a central μ₃‐oxo/alkoxo ligand. These compounds are simultaneously the first nickel derivatives of the 2‐pyridylcyanoxime ligand and the first examples of isolated, μ₃‐O triangular pyridyloximate nickel complexes. Magnetic measurements reveal antiferromagnetic interactions promoted by the μ₃‐O and oximato superexchange pathways and comparison of the experimental structural and magnetic data with DFT calculations give an in‐depth explanation of the factors that determine the magnetic interaction in this kind of system.     

[Zn2(thf)2(EtZn)6Zn4(μ4‐O)(tBuPO3)8]: A Dodecanuclear Zincophosphonate Aggregate with a Zn4(μ4‐O) Core

The largest multinuclear zinc framework synthesized is in the title compound (see picture), which contains structural features closely related to the motifs found in layered and three‐dimensional zincophosphates and zincophosphonates. The reactive centers make this zincophosphonate a viable precursor for the synthesis of porous zincophosphonate materials.     

A Cyclic Hexanuclear Heterometalladithiolene Cluster [{(Cp*Rh)2Mo(μ‐CO)2(CO)}2(S2C6H2S2)2] with Two π‐Conjugated S2C6S2 Bridges: Synthesis,Crystal Structure,and Properties

Two dragons playing ball : Direct metal–metal bond formation using a π‐conjugated dinuclear metalladithiolene complex with two electron‐deficient metal centers as building blocks led to a cyclic double trinuclear heterometalladithiolene cluster with two parallel plane bridges (see structure; Rh pink, Mo green, S yellow, C gray, O red).

     

一个二维Honeycomb-like聚合簇合物 (Et4N)3{[MoS4Cu2(m-CN)]2(m’-CN)}·2MeCN的合成和晶体结构

采用一个预制的簇合物(Et₄N)₂[MoS₄(CuCN)₂]·H₂O(1)和HAc在MeCN中混合反应，生成了一个有趣的二维聚合簇合物(Et₄N)₃{[MoS₄Cu₂(m-CN)]₂(m’-CN)}·2MeCN (2)。通过元素分析，红外光谱及单晶X-射线衍射分析对簇合物2进行了表征。在2的结构中，前驱体1中的MoS₄Cu₂簇核得到了保留，并且此簇核作为三重连接点通过单一氰桥和其他相同的簇核相连，形成一个阴离子型的2D (6,3)（蜂窝状）网络。由预制的簇合物1通过醋酸诱导形成的超分子2表明这种简单的合成方法有可能应用到许多其他相关的体系。     

Neutral and Cationic Hexanuclear Rhenium Phosphine Clusters with μ3‐(Phosphido‐Chalcogenido), μ3‐(Arsenido‐Chalcogenido), and μ3‐(Imido or Oxo‐Chalcogenido) Hetero Ligand Shells

Reactions of dry THF/MeCN solutions of Ca[Re₆SCl(Cl^a)₆] with silylated derivatives E(SiMe₃)₂ (E = PhAs, PSiMe₃, HN, O, S) and addition of trialkylphosphine PPr₃ afford in high yields and at room temperature either the neutral clusters [Re₆SX(PPr₃)] ( 1 : X = As, 2 : X = P) or the ionic compounds [Re₆SX(PPr₃)]²⁺ · [Re₆S₆Cl₈]^2– ( 3 : X = NH, 4 : X = O, 5 : X = S). The compounds 1 – 5 were characterised by X‐ray crystal structure analysis. A di‐substitution reaction occurs on the {Re₆SCl}⁴⁺ cluster core, where the two inner μ₃‐chloro ligands Clⁱ are substituted by X (X = As, P, NH, O, S) and all six terminal chloro ligands Cl^a are exchanged by terminal PPr₃‐ligands.     

An Unexpected Layered Structure in Inorganic Cyanide Clusters: [Cu4(μ3-OH)4][Re4(μ3-Te)4(CN)12]

Diffusion of aqueous solutions of K₄[Re₄Te₄(CN)₁₂] and CuCl₂ in the opposite direction through silica gel gives rise to the new polymer-like compound 1 . This complex has a layered structure built from the interconnected cubane-like cluster cations [Cu₄(μ₃-OH)₄]⁴⁺ and the cluster anions [Re₄Te₄(CN)₁₂]⁴⁻ (see picture).