Ionic liquids are salts that are liquid at low temperature (<100 degrees C) which represent a new class of solvents with nonmolecular, ionic character. Even though the first representative has been known since 1914, ionic liquids have only been investigated as solvents for transition metal catalysis in the past ten years. Publications to date show that replacing an organic solvent by an ionic liquid can lead to remarkable improvements in well-known processes. Ionic liquids form biphasic systems with many organic product mixtures. This gives rise to the possibility of a multiphase reaction procedure with easy isolation and recovery of homogeneous catalysts. In addition, ionic liquids have practically no vapor pressure which facilitates product separation by distillation. There are also indications that switching from a normal organic solvent to an ionic liquid can lead to novel and unusual chemical reactivity. This opens up a wide field for future investigations into this new class of solvents in catalytic applications.

Ionic Liquids-New "Solutions" for Transition Metal Catalysis.

Characterization and comparison of hydrophilic and hydrophobic room temperature ionic liquids incorporating the imidazolium cation

http://yaghi.berkeley.edu/pdfPublications/04MOFs.pdf

Metal-organic frameworks: a new class of porous materials

Carbon capture and storage (CCS) is broadly recognised as having the potential to play a key role in meeting climate change targets, delivering low carbon heat and power, decarbonising industry and, more recently, its ability to facilitate the net removal of CO2 from the atmosphere. However, despite this broad consensus and its technical maturity, CCS has not yet been deployed on a scale commensurate with the ambitions articulated a decade ago. Thus, in this paper we review the current state-of-the-art of CO2 capture, transport, utilisation and storage from a multi-scale perspective, moving from the global to molecular scales. In light of the COP21 commitments to limit warming to less than 2 °C, we extend the remit of this study to include the key negative emissions technologies (NETs) of bioenergy with CCS (BECCS), and direct air capture (DAC). Cognisant of the non-technical barriers to deploying CCS, we reflect on recent experience from the UK's CCS commercialisation programme and consider the commercial and political barriers to the large-scale deployment of CCS. In all areas, we focus on identifying and clearly articulating the key research challenges that could usefully be addressed in the coming decade.

/pdf/carbon-capture-and-storage-ccs-the-way-forward-11rgsqyer0.pdf

Carbon capture and storage (CCS): the way forward

Polycatenation, polythreading and polyknotting in coordination network chemistry

The feasibility of the titled reactions for the rapid, enantioselective synthesis of cis-tricyclo[9.3.1.03,8]pentadecane precursors to taxusin and taxol has been examined. The catalysts most well suited to inducing the appropriate 1,2-shifts have been identified. To a great extent, the rearrangement products are formed as a direct consequence of appropriate structural features (kinetic phenomenon) and strain minimization (thermodynamic driving force). Complementary MM2 calculations of the global minimum in each series provided indications that were completely in line with the experimental observations. Sophisticated NMR studies and X-ray crystallographic determinations were coordinated to remove any ambiguity of product structure and solid-state conformation.

An Enantioselective Approach to the Taxanes: Direct Access to Functionalized cis-Tricyclo(9.3.1.03,8)pentadecanes via α- Hydroxy Ketone and Wagner-Meerwein Rearrangements.

The preparation and binding properties of spirocyclic tetrahydrofurans 7-11 are described. The condensition of cyclopentanone with 5-lithio-2,3-dihydrofuran (12) provided an alcohol which readily rearranged to ketone 14 under acidic condition. »Capping« of the carbonyl group in 14 so as to generate a second spiro tetrahydrofuran subunit gave rise to 7 and 8. Starting with cyclobutanone, 2-fold ring expansion involving 12 provided the key reaction leading to 22 and 23, which were »capped« as before

Synthesis and Molecular Structure of Belted Spirocyclic Tetrahydrofurans, a New Class of Preorganized Hosts for Cations.

We have initially developed methodology amenable to the convenient preparation of the trispiro isomers 3-5 shown herein and have elucidated their solid-state conformational features. Furthermore, the binding properties of 3-5 have been compared to those of their previously unknown lower homologues 6 and 7

Belted Spirocyclic Tetrahydrofurans: A New Class of Preorganized Ionophoric Polyethers. Molecular Structure, Conformation, and Binding to Alkali‐Metal Atoms.

Oxonium ylides were formed via an intramolecular reaction between a series of dioxalanes and metallocarbenes. The substitution patterns present in the ketals greatly affect the rearrangements of the oxonium ylides. It was also demonstrated that electron-deficient copper (II) species are superior catalysts for these systems.

Selectivity in the Rearrangements of Oxonium Ylides.

Cycloaddition of 3-oxido-1-phenylpyridinium 8a to 1-cyanoacenaphthylene 9a affords three isomeric adducts (13, 14 and 15). Structures for these compounds resulted from a comparative NMR study, as well as an X-ray crystallographic determination of isomer 15. Attempts to eliminate HCN from compounds 13–15 resulted only in cycloreversion to 1-cyanoacenaphthylene.

Robin D. Rogers

Papers

An Enantioselective Approach to the Taxanes: Direct Access to Functionalized cis-Tricyclo(9.3.1.03,8)pentadecanes via α- Hydroxy Ketone and Wagner-Meerwein Rearrangements.

Synthesis and Molecular Structure of Belted Spirocyclic Tetrahydrofurans, a New Class of Preorganized Hosts for Cations.

Belted Spirocyclic Tetrahydrofurans: A New Class of Preorganized Ionophoric Polyethers. Molecular Structure, Conformation, and Binding to Alkali‐Metal Atoms.

Selectivity in the Rearrangements of Oxonium Ylides.

Cycloaddition Products of 3-Oxido-1-phenylpyridinium and 1-Cyanoacenaphthylene.