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BACKGROUND INFORMATION

Hon. B.Sc., McMaster University. M.A., Ph.D., University of Toronto.                               

Postdoctoral Fellow, Imperial College, London (with Prof. G. Wilkinson, FRS, Nobel Laureate).

Alexander von Humboldt Fellow, Technical University, Munich, 1975 (with Prof. E. O. Fischer, Nobel Laureate).                             

Fellow of the Chemical Institute of Canada.      

Chemistry Department Excellence in Teaching Award, 1982, 1989, 2002, 2003, 2009.                    

Alcan Lecture Award of the Chemical Institute of Canada, 1986.                                      

Inducted into the McMaster University Sports Hall of Fame, 1997.     

Prize for Excellence in Research, Queen's University, 1998.                                         

Catalysis Award of the Chemical Institute of Canada, 2002.                                                

Inaugural Inductee, Queen's University Athletic Coaches Hall of Fame, 2003.                

Elected Fellow of the Royal Society of Canada, 2003.

Canadian Catalysis Lectureship Award of the Canadian Catalysis Foundation and the Chemical Institute of Canada, 2009                                      

RESEARCH INTERESTS

Many branches of chemistry and materials science now interface with organometallic chemistry - the study of compounds containing carbon-metal bonds. Thus organometallic chemistry research in our lab is interdisciplinary in nature and involves research on aspects of inorganic, organic, polymer, and catalysis chemistry. As outlined below and on the linked pages, we are currently working on a wide variety of research projects which offer opportunities for students and PDFs to gain both useful scientific knowledge and also experience with a number of important spectroscopic and analytical tools.

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Specific Projects

Synthetic Organometallic Chemistry 

We have over the past few years synthesized a number of 17-electron organometallic compounds and a series of new metal-fullerene compounds; the compounds had not been previously made and we were curious to see if we could make them and what they would be like. We have also recently prepared a number of organotitanium and organopalladium compounds because we anticipated that they would either function as very interesting new  catalysts or that they would exhibit novel chemistry. 

Research based on this philosophy continues with syntheses of a variety of new cyclopentadienylidene ligands such as the following (R, R', R" = alkyl, aryl):

One or two ylids of this type were prepared many years ago, and one of them was shown to coordinate to metal ions via the pseudo-cyclopentadienyl group. Although the mode of bonding is intermediate between those of neutral arene  and anionic cyclopentadienyl ligands, thus probably resulting in a wealth of as yet undiscovered chemistry, in fact this class of compounds has been little studied. We are addressing this failure, uncovering a variety of new compounds which have never previously seen the light of day. We shall in the near future assess several of these for potential catalytic properties and others as anti-cancer drugs.

Of great potential interest, one of our new types of ligand exhibits planar chirality and thus forms chiral complexes on coordination as in the recently published the chromium compound shown here.

The chirality is very close to the metal in such species, and current work involves the syntheses of analogous chiral complexes of titanium and ruthenium which are expected to exhibit fascinating properties as catalysts, including the ability to effect asymmetric syntheses.

Molecular orbital of a chromium cyclopentadienylidene complex

Rational Syntheses of Metallocarbohedrynes     (Met-cars)

Blue atoms carbon, red & grey atoms titanium

One of the most interesting recent developments in chemistry has been the plasma synthesis and gas phase mass spec detection of met-cars such as the cluster compound Ti₈C₁₂. Although Ti₈C₁₂ has not yet been synthesized in macroscopic quantities, it probably has the structure illustrated above. It has, however, been shown experimentally to have an ionization potential comparable to those of atomic sodium and potassium (!!!) and to (somehow) readily absorb up to four molecules of methane per molecule of cluster at temperatures as high as –60 °C. In addition, high quality computational studies predict that Ti₈C₁₂ will be found to  reversibly absorb up to 16 molecules of H₂ per molecule of cluster to yield a material containing ~6 % H₂ by weight and  giving rise to the possibility that the adducts will be useful as new high capacity hydrogen storage systems. We are currently developing rational syntheses of met-cars such as Ti₈C₁₂ with a view to studying their chemistry. In view of their incredibly low ionization potentials they should form fascinating nanomaterials. Their chemistry with methane will also be studied as they may provide catalytic routes to the functionalization of this very inexpensive feed-stock, and their properties as novel high capacity hydrogen storage systems and hydrogenation catalysts will be investigated.

One of our molecules from the past.

        Contact Information

         Professor Mike Baird                                        
         Department of Chemistry,
         Chernoff Hall, Queen's University,
         90 Bader Lane,
         Kingston, ON K7L 3N6
        
         Room: CHE 402 (Office), CHE 434 (Lab) 
         Office Telephone: 613-533-2614  
         Laboratory Telephone: 613-533-6000  ext. 74669  
         Fax: 613-533-6669

          e-mail: bairdmc@chem.queensu.ca

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Projects to be initiated over the  next  year or so will  give  new  graduate students opportunities to synthesize interesting organometallic compounds which have never been prepared before, to explore the use of organometallic compounds as catalysts for "green" chemistry and for making plastics biodegradable, to develop new initiators for polymer synthesis and to develop new catalytic applications of organometallic compounds to both  industrial processes and organic synthesis.

Alkene Polymerization

Organometallic compounds which initiate and catalyze alkene polymerization are of enormous academic and commercial interest, and we have recently discovered a class of organotitanium compounds which exhibit remarkable properties as polymerization catalysts. We are also very active in the development of catalytic procedures for making new types of polymers and in studying mechanisms of transition metal catalyzed olefin polymerization processes.

Polyethylene is a major commodity plastic, with over 60 million tonnes being produced worldwide annually. Most PE consists of either essentially linear CH₃(CH₂)_nCH₃ (n = very large integers), or similar materials with random distributions of n-butyl or n-hexyl branches. A limitation of these materials is that they are really just saturated hydrocarbons and thus they do not bind to polar surfaces and they are insoluble in polar media. There is therefore considerable interest in the synthesis of PE containing polar functionality, and in research which is still in its early stages we are devising methodologies for the incorporation into PE of variable length branches containing terminal OH groups. The new materials being prepared are expected to exhibit many useful properties such as paintability, adhesion to polar surfaces, miscibility with e.g. polyesters and polyamides. They should also be biodegradable, which would be of enormous environmental benefit since they may well provide  biodegradable alternatives to the currently used non-biodegradable polyethylene grocery and garbage bags.

The interesting thing about much of this research is that we anticipate discovering both new and better catalysts for the synthesis of known materials and also new polymeric materials. We are working successfully in both directions. There is scope here for new students to become knowledgeable of catalysis in addition to polymer synthesis and characterization, all useful when seeking employment.

"Green" Catalysis, Synthetic Fuels

An area in which research in our lab is currently beginning is concerned with the catalytic hydrogenation of esters and amides, i.e.

RCO₂R' + 2H₂      RCH₂OH + R'OH

RCONR'₂ + 2H₂   RCH₂NR'₂ + H₂O

Reduction of these types of substrates is usually effected stoichiometrically using hydride sources such as LiAlH₄, in which case there are also produced considerable amounts of very corrosive, undesirable byproducts. However, the very recent literature describes a small number of transition metal compounds which effectively catalyze the hydrogenation reactions shown above, giving the same types of products obtained via hydride reduction but forming no byproducts. Those catalysts which are successful generally contain rather complex ligands, however, and it seems likely that broad use of new catalytic protocols will require easier to synthesize (less expensive) catalysts. Accordingly we have begun to explore the catalytic activities of a series of candidate transition metal compounds, anticipating that new, green catalysts for this reaction will be found.

Success in these endeavors may also result indirectly in the development of new synthetic fuels technologies. Most students are aware of the need for alternative fuels in the future and of the fact that there is a huge and growing interest in the use of ethanol-gasoline blends. What is not generally recognized is that while there are sound scientific reasons for using ethanol in this way, much of the current interest in ethanol as a fuel is driven politically by agricultural interests attempting to develop markets for “bioethanol”. There are, however, many well known and much debated problems associated with the concept, not the least of which is a growing disinclination to use food resources to provide fuel for automobiles. Thus, while governments in North America and Europe have recently embraced the idea of ethanol-gasoline blends, alternative methodologies for the manufacture of fuel ethanol are desirable and are probably achievable via new processes utilizing transition metal catalysts. We shall soon begin research on the synthesis of fuel ethanol via routes which are more efficient (“greener”) than are currently utilized manufacturing processes, with a view to being able to have a useful technology for fuel ethanol manufacture in place at the time when bioethanol is realized to be commercially uncompetitive for most large scale industrial purposes. In addition, of course, if ethanol were to become more available at a lower price, non-fuel applications would likely also become important.