Dalton Transactions

doi: 10.1039/b907087gpmid: N/A

doi: 10.1039/b907088ppmid: N/A

Molski, Matthias Johann; Seppelt, Konrad

doi: 10.1039/b821121cpmid: 19381398

The nine transition metal hexafluorides present a unique series of closely related compounds. Deviations from octahedral structures are influenced by Jahn–Teller effects and spin orbit coupling. The most pronounced chemical behaviour is the increasing electron affinity in the direction WF6→ PtF6 and MoF6→ RuF6, so that with PtF6 and RuF6 values of 7 eV or higher are reached. All hexafluorides can be used as one electron oxidants, starting with mild (WF6) up to extreme (PtF6, RuF6) oxidation power.

Dewhurst, Rian D.; Hill, Anthony F.; Willis, Anthony C.

doi: 10.1039/b900205gpmid: 19381399

The reactions of Vaska's complex with [Hg{CCCW(CO)2(L)}2] (L = HB(pz)3, HB(pzMe2)3, pz = pyrazol-1-yl) unexpectedly provide the structurally characterized tetrametallic trans-bis(tricarbido)complex [Ir(HgCl){CCCW(CO)2(L)}2(CO)(PPh3)2].

Karotsis, Georgios; Stoumpos, Constantinos; Collins, Anna; White, Fraser; Parsons, Simon; Slawin, Alexandra M. Z.; Papaefstathiou, Giannis S.; Brechin, Euan K.

doi: 10.1039/b902002kpmid: 19381400

The use of α–benzoin oxime in Ni(II) chemistry leads to the formation of a family of unusual molecular and supramolecular wheels.

O'Neill, Megan K.; Trappey, Alfred Francois; Battle, Paul; Boswell, Christopher L.; Blauch, David N.

doi: 10.1039/b902513hpmid: 19381401

Oxidation of [Ru(NH2Q)3]2+ (NH2Q = 8-aminoquinoline) results in intermolecular coupling of 8-aminoquinoline ligands to yield an electroactive polymer. Oxidative polymerization is not observed for [Ru(bpy)2(NH2Q)]2+ (bpy = 2,2′-bipyridine), where only one 8-aminoquinoline ligand is present.

Cui, Xiangzhi; He, Qianjun; Cui, Fangming; Zhao, Jinjin; Li, Lei; Chen, Hangrong; Shi, Jianlin

doi: 10.1039/b816573dpmid: 19381402

A well-crystallized mesoporous hydrous ruthenium dioxide (RuOxHy) with high surface area of 120 m2 g−1 and high electrochemical catalytic activity has been synthesized by a replicating route with the mesoporous silica (KIT-6) as hard template. The materials were characterized by means of thermo-gravimetric analysis (TG), X-ray diffraction (XRD), field emission scanning electron microscopy (FE-SEM), transmission electron microscopy (TEM) and N2 sorption. The electrocatalytic activity of the samples for methanol oxidation were investigated by cyclic voltammetry (CV) and linear scan voltammetry (LSV) techniques. A mixed gas of CO and O2 was adopted to investigate the effect of gas treatment on the electrochemical activity of the samples. The results show that the electrocatalytic activity of the prepared mesoporous RuOxHy and 3 wt% Pt/mesoporous RuOxHy toward methanol oxidation was much enhanced after treatment with a mixed gas of CO and O2. The enhanced electrochemical catalytic activity of the materials might be attributed to the structure activation during the gas treatment and the high surface area of RuOxHy matrix with mesoporous structure.

Inglis, Ross; Jones, Leigh F.; Milios, Constantinos J.; Datta, Saiti; Collins, Anna; Parsons, Simon; Wernsdorfer, Wolfgang; Hill, Stephen; Perlepes, Spyros P.; Piligkos, Stergios; Brechin, Euan K.

doi: 10.1039/b822235e

Vautravers, Nicolas R.; André, Pascal; Cole-Hamilton, David J.

doi: 10.1039/b820349kpmid: 19381404

New diazaphospholidine POSS macromolecules have been synthesised and tested in styrene and vinyl acetate hydroformylation. Whilst some of them have shown activity, others precipitated upon mixing with the rhodium precursor preventing its efficient use. Molecular dynamics has been used to help understand these observations. Rigid and compact dendritic structures with phosphine groups engineered to have low mobility but high probability of sitting at distances favouring bidentate coordination with the rhodium precursors are necessary for the macromolecular ligands to be active. More flexible structures having lower probability of phosphine separations suitable for bidentate complex formation are more prone to form oligomeric dendritic species and hence to crosslink the macromolecules and precipitate.

Wei, Zhen-Hong; Li, Hong-Xi; Ren, Zhi-Gang; Lang, Jian-Ping; Zhang, Yong; Sun, Zhen-Rong

doi: 10.1039/b822858bpmid: 19381405

Stepwise reactions of [Et4N][Tp*WS3] (1) (Tp* = hydridotris(3,5-dimethylpyrazol-1-yl)borate) with 1–4 equiv. of CuNCS (and Et4NBr in the case of three equiv. of CuNCS) afforded the [1 + 1] to [1 + 4] addition products [Et4N][Tp*WS(μ-S)2(CuNCS)]·0.5CH2Cl2 (2·0.5CH2Cl2), [Et4N][Tp*W(μ3-S)(μ-S)2(CuNCS)2]·ClCH2CH2Cl (3·ClCH2CH2Cl), [Et4N]2[Tp*W(μ3-S)3(CuNCS)3(μ3-Br)]·1.5aniline (4·1.5aniline), and {[Et4N][Tp*W(μ3-S)3(Cu-μ-SCN)3(Cu-μ3-NCS)]}n (5). Compounds 2–5 were characterized by elemental analysis, IR spectra, UV-vis spectra, 1H NMR, and single-crystal X-ray crystallography. The cluster anion of 2 contains a [WS2Cu] core formed by addition of one CuNCS group onto the [Tp*WS3] species. The cluster anion of 3 has a butterfly-shaped [WS3Cu2] core constructed by addition of two CuNCS groups onto the [Tp*WS3] species. The cluster dianion of 4 consists of a cubane-like [Tp*WS3Cu3(μ3-Br)] core assembled by addition of three CuNCS groups onto the [Tp*WS3] species followed by filling a μ3-Br into the void of the incomplete cubane-like [Tp*WS3(CuNCS)3] fragment. 5 has a 2D cluster-supported layer network in which each [Tp*WS3Cu3] core acting as a pyramidal 3-connecting node interconnects with the [Cu(NCS)4] units through thiocyanate bridges. In addition, the third-order nonlinear optical (NLO) performances of 2–5 in DMF were also investigated by Z-scan techniques.