Dr Alan Brisdon MRSC, CChem

Senior Lecturer

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Research interests

Keywords: fluorine chemistry | synthesis | spectroscopy | fluorophosphines | fluorographene | organofluorometallics

Our research falls under the umbrella description of "Fluorine Chemistry", a specialist area of chemistry for which universities in Manchester have a long-standing, and ongoing, national and international reputation. [For example the world famous electrophillic fluorinating agent Selectfluor was first prepared and its chemistry developed, in Manchester]. We deliberately deal with aspects that straddle the traditional inorganic and organic boundaries. We study many different areas including main-group, transition-metal, organometallic and organofluorine chemistry. In addition we are interested in the structure/property relationships of these systems using Xray diffraction and multinuclear NMR methods (amongst others). We also work in more applied areas of fluorine-containing materials, such as ionic liquids and fluorographenes.

Most of this work, unless commercially sensitive, is published in international peer-reviewed journals, in addition, below is a selection of recent fluorine-related textbooks written by internationally-reknowned fluorine chemists, where you will find our work cited:

front cover from Peer Kirsch's book front cover from Kenji Uneyama's book front cover of Dick Chamber's book front cover of Horvath's book

 

Below you will find brief details of the areas of fluorine research in which we are currently engaged; more comprehensive information, a full set of publications and research tools and calculators (such as the microanalysis [percentage composition], mass spec isotope patterns and 31-P NMR chemical shift and multiplet pattern calculators) are available on the fluorine web server.

 

Fluorinated Phosphines

Keywords: fluoroakynyl | fluoroalkenyl | fluoroalkyl | phosphines | methodology | metal complexes | catalysis.

A major theme of our research concentrates on making new organofluorine-containing phosphorus(III) systems because such ligands show a unique combination of steric and electronic properties, often along with enhanced thermal and oxidative stability, suitable for catalytic applications.

In addition to the HFC routes described above (eg to give PR2(CF=CF2), PR2(CCl=CF2), PR2(CF=CFH), PR(CCCF3)2 etc.) We have developed a generic method for introducing fluoroalkyl ligands into phosphines, to give new fluoroalkyl-containing phosphines, such as Ph2P(i-C3F7), shown below, which is the first reported phospine containing a secondary fluoroalkyl group. We have also reported perfluoro- t-Bu, Cy and many other sterically demanding electron-withdrawing groups.

Xray structure of Ph2P(i-C3F7), a secondary fluoroalkyl phosphine

By modifying the fluorinated group we can change the steric and electronic effects at the phosphorus centre and so modify the ligand's properties, and this we study via coordination chemistry  and spectroscopy. We also prepare main-group and transition-metal systems containing these ligands and investigate their applications in catalysis.

We have also investigated new synthetic routes to fluoro-phosphites, and related compounds; again these can be used as ligands which we can readily modify the steric, electronic and solvency effects, and generated unusual packing motifs for inorganic systems.

Fluorinecontaining materials

Keywords:  ionic liquids | RTILs | fluorographene | synthesis | properties.

We are interested in the effects of introducing fluorine into molecules to generate fluorinated materials. For example, Ionic Liquids (ILs) are compounds entirely composed of ions that are liquid at, or below 100 C. Room temperature ionic liquids (RTILs) belong to the same class of materials, but are liquid at room temperature. These liquids are beginning to find industrial applications in a wide variety of areas, including as paint additives, electrolytes, extraction and gas transport. We have been working on asymmetric and fluorine-containing room temperature ionic liquids which possess wide electrochemical windows, one such example is shown below. They can be used to control solvency and an example is the three-phase ionic liquid-water-organic solvent system shown below.

[An asymmetric ammonium-based room temperature ionic liquid]A three phase ionic-liquid/water/organic solvent system.

We have been studying the fluorination of graphenes for some time, and have prepared fluorographenes across a wide range of C:F ratios. Our current work in this area involves extending our methodology and an investigation of their applications and is supported by venture capital funding.

Fluorographene

Organofluorine Chemistry

Keywords: organofluorine methodology | fluorine building blocks | fluoro-organometallic | metal complexes.

We are one of the world-leading groups working on the use & development of hydrofluorocarbons (HFCs) as a convenient source of introducing small fluorocarbon groups into systems. In particular we have developed methodology based on the readily-available HFCs (which are non-ozone-deleting CFC-replacements) to generate accessible organofluorine building blocks. These reagents have been used for the synthesis of main-group and transition metal elements. For example HFC-134a (CF3CH2F) gives perfluorovinyllithium (CF2=CFLi). Via this route we have obtained, for the first time, a number of structurally characterised fluorovinyl-containing metal and organometallic compounds.

X-ray structure of fluorovinyl-containing transition-metal complexes

We similarly developed routes to fluoroalkynyl substituents, such as CF3CC- based on the hydrofluorocarbon CF3CH2CHF2 (HFC-245fa). Not only does this provide the method of choice for chemists seeking to introduce the trifluoropropynyl group, but it also is the starting point for much more chemistry, such as derivatisation, cyclisation etc. Indeed, under facile conditions we can convert this to small C-3-cyclised products, such as the gem-difluorocyclopropene system. Other C-3 work has focussed on the organometallic chemistry of pentafluoropropenyl systems and their use in metal-catalysed coupling reactions.

Projects

Research and projects

No current projects are available for public display