Alexander F. R. Kilpatrick

Controlling selectivity in the reductive activation of CO2 by mixed sandwich uranium(III) complexes

The synthesis and molecular structures of a range of uranium(III) mixed sandwich complexes of the type [U(η8-C8H6(1,4-SiMe3)2)(η5-CpMe4R)] (R = Me, Et, iPr, tBu) and their reactivity towards CO2 are reported. The nature of the R group on the cyclopentadienyl ring in the former has a significant effect on the outcome of CO2 activation: when R = Me, the products are the bridging oxo complex {U[η8-C8H6(1,4-SiMe3)2](η5-CpMe5)}2(μ-O) and the bridging oxalate complex {U[η8-C8H6(1,4-SiMe3)2](η5-CpMe5)}2(μ-η2:η2-C2O4); for R = Et or iPr, bridging carbonate {U[η8-C8H6(1,4-SiMe3)2](η5-CpMe4R)}2(μ-η1:η2-CO3) and bridging oxalate complexes {U[η8-C8H6(1,4-SiMe3)2](η5-CpMe4R)}2(μ-η2:η2-C2O4) are formed in both cases; and when R = tBu the sole product is the bridging carbonate complex {U[η8-C8H6(1,4-SiMe3)2](η5-CpMe4tBu)}2(μ-η1:η2-CO3). Electrochemical studies on both the uranium(III) complexes and the dimeric uranium(IV) CO2 reduction products have been carried out and all exhibit quasi reversible redox processes; in particular, the similarities in the U(III)/U(IV) redox couples suggest that the selectivity in the outcome of CO2 reductive activation by these complexes is steric in origin rather than electronic. The latter conclusion is supported by a detailed computational DFT study on the potential mechanistic pathways for reduction of CO2 by this system.

Bis(pentalene)di-titanium: a bent double-sandwich complex with a very short Ti–Ti bond

The novel bimetallic bis(pentalene) complex Ti2(μ:η(5),η(5)-Pn(†))2 (Pn(†) = C8H4{Si(i)Pr3-1,4}2) has been synthesised and structurally characterised. Structural data show a Ti-Ti distance of 2.399(2) Å, consistent with a strong metal-metal interaction, which DFT calculations best describe as a double bond with σ and π components.

Hydrodeoxygenation of water-insoluble bio-oil to alkanes using a highly dispersed Pd–Mo catalyst

Bio-oil, produced by the destructive distillation of cheap and renewable lignocellulosic biomass, contains high energy density oligomers in the water-insoluble fraction that can be utilized for diesel and valuable fine chemicals productions. Here, we show an efficient hydrodeoxygenation catalyst that combines highly dispersed palladium and ultrafine molybdenum phosphate nanoparticles on silica. Using phenol as a model substrate this catalyst is 100% effective and 97.5% selective for hydrodeoxygenation to cyclohexane under mild conditions in a batch reaction; this catalyst also demonstrates regeneration ability in long-term continuous flow tests. Detailed investigations into the nature of the catalyst show that it combines hydrogenation activity of Pd and high density of both Brønsted and Lewis acid sites; we believe these are key features for efficient catalytic hydrodeoxygenation behavior. Using a wood and bark-derived feedstock, this catalyst performs hydrodeoxygenation of lignin, cellulose, and hemicellulose-derived oligomers into liquid alkanes with high efficiency and yield.Bio-oil is a potential major source of renewable fuels and chemicals. Here, the authors report a palladium-molybdenum mixed catalyst for the selective hydrodeoxygenation of water-insoluble bio-oil to mixtures of alkanes with high carbon yield.

Controlling the Surface Hydroxyl Concentration by Thermal Treatment of Layered Double Hydroxides

Layered double hydroxides (LDHs) are important materials in the field of catalyst supports, and their surface hydroxyl functionality makes them interesting candidates for supporting well-defined single-site catalysts. Here, we report that the surface hydroxyl concentration can be controlled by thermal treatment of these materials under vacuum, leading to hydroxyl numbers (αOH) similar to those of dehydroxylated silica, alumina, and magnesium hydroxide. Thermal treatment of [Mg0.74Al0.26(OH)2](SO4)0.1(CO3)0.03·0.62(H2O)·0.04(acetone) prepared by the aqueous miscible organic solvent treatment method (Mg2.84Al-SO4-A AMO-LDH) is shown to yield a mixed metal oxide above 300 °C by a combination of thermogravimetric analysis, powder X-ray diffraction (PXRD), BET surface area analysis, and FTIR spectroscopy. PXRD shows the disappearance of the characteristic LDH 00l peaks at 300 °C indicative of decomposition to the layered structure, coupled with a large increase in the BET surface area (95 vs 158 m2 g-1 from treatment at 275 and 300 °C, respectively). Titration of the surface hydroxyls with Mg(CH2Ph)2(THF)2 indicates that the hydroxyl number is independent of surface area for a given treatment temperature. Treatment at 450 °C under vacuum produces a mixed metal oxide material with a surface hydroxyl concentration (αOH) of 2.14 OH nm-2 similar to the hydroxyl number (αOH) of 1.80 OH nm-2 for a sample of SiO2 dehydroxylated at 500 °C. These materials appear to be suitable candidates for use as single-site organometallic catalyst supports.

Ring-Opening Polymerisation of Low-Strain Nickelocenophanes: Synthesis and Magnetic Properties of Polynickelocenes with Carbon and Silicon Main Chain Spacers

Polymetallocenes based on ferrocene, and to a lesser extent cobaltocene, have been well-studied, whereas analogous systems based on nickelocene are virtually unexplored. It has been previously shown that poly(nickelocenylpropylene) [Ni(η5 -C5 H4 )2 (CH2 )3 ]n is formed as a mixture of cyclic (6x ) and linear (7) components by the reversible ring-opening polymerisation (ROP) of tricarba[3]nickelocenophane [Ni(η5 -C5 H4 )2 (CH2 )3 ] (5). Herein the generality of this approach to main-chain polynickelocenes is demonstrated and the ROP of tetracarba[4]nickelocenophane [Ni(η5 -C5 H4 )2 (CH2 )4 ] (8), and disila[2]nickelocenophane [Ni(η5 -C5 H4 )2 (SiMe2 )2 ] (12) is described, to yield predominantly insoluble homopolymers poly(nickelocenylbutylene) [Ni(η5 -C5 H4 )2 (CH2 )4 ]n (13) and poly(tetramethyldisilylnickelocene) [Ni(η5 -C5 H4 )2 (SiMe2 )2 ]n (14), respectively. The ROP of 8 and 12 was also found to be reversible at elevated temperature. To access soluble high molar mass materials, copolymerisations of 5, 8, and 12 were performed. Superconducting quantum interference device (SQUID) magnetometry measurements of 13 and 14 indicated that these homopolymers behave as simple paramagnets at temperatures greater than 50 K, with significant antiferromagnetic coupling that is notably larger in carbon-bridged 6x /7 and 13 compared to the disilyl-bridged 14. However, the behaviour of these polynickelocenes deviates substantially from the Curie-Weiss law at low temperatures due to considerable zero-field splitting.