The tungsten-tungsten triple bond---18. Bridging and terminal allyl ligands in complexes of the formula W2(R)2(NMe2)4, where R = C3H5 and C4H7

The reaction between RMgCl (two equivalents) and 1,2-W₂Cl₂(NMe₂)₄ in hydrocarbon solvents affords the compounds W₂R₂(NMe₂)₄, where R = allyl and 1− and 2-methyl-allyl. In the solid state the molecular structure of W₂(C₃H₅)₂(NMe₂)₄ has C₂ symmetry with bridging allyl ligands and terminal W---NMe₂ ligands. The W---W distance 2.480(1) Å and the C---C distances, 1.47(1) Å, imply an extensive mixing of the allyl π-MOs with the WW π-MOs, and this is supported by an MO calculation on the molecule W₂(C₃H₅)₂(NH₂)₄ employing the method of Fenske and Hall. The most notable interaction is the ability of the (WW)⁶⁺ centre to donate to the allyl π^*-MO (π₃). This interaction is largely responsible for the long W---W distance, as well as the long C---C distances, in the allyl ligand. The structure of the 2-methyl-allyl derivative W₂(C₄H₇)₂(NMe₂)₄ in the solid state reveals a gauche-W₂C₂N₄ core with W---W = 2.286(1) Å and W---C = 2.18(1) Å, typical of WW and W---C triple and single bonds, respectively. In solution (toluene-d₈) ¹H and ¹³C NMR spectra over a temperature range −80°C to +60°C indicate that both anti- and gauche- W₂C₂N₄ rotamers are present for the 2-methyl-allyl derivative. In addition, there is a facile fluxional process that equilibrates both ends of the 2-methyl-allyl ligand on the NMR time-scale. This process leads to a coalescence at 100°C and is believed to take place via an η³-bound intermediate. The 1-methyl-allyl derivative also binds in an η¹ fashion in solution and temperature-dependent rotations about the W---N, W---C and C=C bonds are frozen out at low temperatures. The spectra of the allyl compound W₂(C₃H₅)₂(NMe₂)₄ revealed the presence of two isomers in solution—one of which can be readily reconciled with the presence of the bridging isomer found in the solid state while the other is proposed to be W₂(η³-C₃H₅)₂(NMe₂)₄. The compound W₂R₂(NMe₂)₄ where R = 2,4-dimethyl- pentadiene was similarly prepared and displayed dynamic NMR behaviour explainable in terms of facile η¹ = η³ interconversions.     

Rational and Heron tetrahedra

Buchholz [R.H. Buchholz, Perfect pyramids, Bull. Austral. Math. Soc. 45 (1991) 353-368] began a systematic search for tetrahedra having integer edges and volume by restricting his attention to those with two or three different edge lengths. Of the fifteen configurations identified for such tetrahedra, Buchholz leaves six unsolved. In this paper we examine these remaining cases for integer volume, completely solving all but one of them. Buchholz also considered Heron tetrahedra, which are tetrahedra with integral edges, faces and volume. Buchholz described an infinite family of Heron tetrahedra for one of the configurations. Another of the cases yields a new infinite family of Heron tetrahedra which correspond to the rational points on a two-parameter elliptic curve.     

Electronically-coupled tungsten-tungsten quadruple bonds: comparisons of electron delocalization in 3,6-dioxypyridazine and oxalate-bridged compounds

The preparation of the 3,6-dioxypyridazine-bridged tungsten complex, [W(2)(O(2)C(t)Bu)(3)](2)(mu-H(2)C(4)N(2)O(2)), I, is described, along with its single-electron oxidized cation, I(+), formed in the reaction between I and Ag(+)PF(6)(-). Compound I has been structurally characterized as a PPh(3) adduct, and I(+)PF(6)(-) as a THF solvate, by single-crystal X-ray studies. The geometric parameters of these compounds compare well with those calculated for the model compounds [W(2)(O(2)CH)(3)](2)(mu-H(2)C(4)N(2)O(2)) and [W(2)(O(2)CH)(3)](2)(micro-H(2)C(4)N(2)O(2))(+) by density functional theory employing the Gaussian 98 and 03 suite of programs. The calculations indicate that the two W(2) centers are strongly coupled by M(2) delta-to-bridge pi-bonding, and further coupled by direct M(2)...M(2) bonding. Compound I is purple and shows an intense absorption in the visible region due to a metal-to-bridge charge transfer and, with excitation within this absorption, compound I exhibits pronounced resonance Raman bands associated with symmetric vibrations of the bridge and the M(4) unit. The cyclic voltammogram of I in THF, the EPR spectrum of I(+)PF(6) in 2-MeTHF and the electronic absorption spectrum of I(+)PF(6)(-) in THF are consistent with electron delocalization over both W(2) units. These new data are compared with previous data for the molybdenum analogue, related oxalate-bridged compounds and closely related cyclic polyamidato-bridged Mo(4)-containing compounds. It is proposed that, while the electronic coupling occurs principally by an electron-hopping mechanism for oxalate-bridged compounds, hole-hopping contributes significantly in the cases of the amidate bridges and that this is more important for M = Mo than for M = W. Furthermore, for Class III fully delocalized mixed-valence compounds, the magnitude of K(c), determined from electrochemical methods, is not necessarily a measure of the extent of electron delocalization.     

Gas-phase and solution-phase polymerization of epoxides by Cr(salen) complexes: evidence for a dinuclear cationic mechanism

The gas-phase reactions of a series of mass-selected mononuclear and dinuclear Cr(salen) complexes with propylene oxide suggest that the enhanced reactivity of the dinuclear complexes in gas-phase and in solution may derive from a dicationic mechanism in which the alkoxide chain is mu(2)-coordinated to two Lewis acidic metal centers. The double coordination is proposed to suppress backbiting, and hence chain-transfer in the gas-phase homopolymerization of epoxides.     

Two-phase flow in bends

An equation is developed for use in predicting the two-phase multiplier for pressure drop in bends; the equation simplifies the use of an existing method. The method is also compared for the first time with data at high density ratios ($\text{?l/?g = 560}$).     

Concerning the relative importance of enantiomorphic site vs. chain end control in the stereoselective polymerization of lactides: reactions of (R,R-salen)- and (S,S-salen)-aluminium alkoxides LAlOCH2R complexes (R = CH3 and S-CHMeCl)

The preparations and structures of LAlOCH(2)C(S)HMeCl, where L = (R,R) or (S,S)-N,N'-bis(3,5-di-tert-butyl-salicylidene)-1,2-cyclohexenediamino, are reported together with the respective LAlOEt compounds, and their reactivities toward L- and rac-lactides in various solvents reveal the surprising complexity of the stereopreference for the ring-opening event.     

Combinatorial materials research applied to the development of new surface coatings: VIII: Overview of the high-throughput measurement systems developed for a marine coating workflow

A combinatorial workflow has been produced for the development of novel, environmental-friendly marine coatings. A particularly challenging aspect of the workflow development was the selection and development of high-throughput screening methods that allow for some degree of prediction of coating performance in the aquatic environment of interest. The high-throughput screening methods currently in place include measurements of surface energy, viscoelastic properties, pseudobarnacle adhesion, and a suite of biological assays based on various marine organisms. An experiment involving a series of fouling-release coatings was used to correlate high-throughput screening data to data obtained from ocean site immersion testing. The results of the experiment showed that both bacterial biofilm surface coverage and storage modulus at 30 °C showed a good correlation with barnacle adhesion strength and a fair correlation with fouling rating, but surface energy and pseudobarnacle adhesion did not correlate with the results from ocean site testing.     

Mössbauer Studies of Electrodeposited and Ion Beam Mixed Alloy Coatings

CEMS, XMS, XRD and electron microprobe analysis were applied to study electrodeposited and ion beam mixed Fe–Cr–Ni as well as electrodeposited and ball-milled Sn–Cr alloys. In Fe–Cr–Ni alloys with composition 40% Cr and 20–30% Ni a metastable ferromagnetic phase has been found beside a metastable paramagnetic and an equilibrium phase in all deposits. The relative occurrence of the ferromagnetic phase exhibits an increase in the plating temperature range: 30–40°C. With plating temperature an increase of the short-range order in the ferromagnetic phase was observed. The highenergy heavy ion irradiation of Fe–Ni–Cr multilayer produces ferromagnetic and paramagnetic metastable phases. The electrodeposition of Sn–Cr alloys results in metastable Sn–Cr phases. In the case of ball-milling preparation the equilibrium Sn₃Cr₂ phase (=2.3 mm/s, =1.2 mm/s) appears in Sn–Cr alloys. The quantity of the Sn₃Cr₂ phase increases with the milling time.