Academic Profile

Academic Profile

Prof Francois Mathey

Division of Chemistry & Biological Chemistry
School of Physical & Mathematical Sciences
College of Science

Phone: (+65)65132731
Office: SPMS-CBC-06-08

  • PhD Uni Paris VI (Pierre et Marie Curie) 1971
  • MS Uni Paris VI (Pierre et Marie Curie) 1965
  • BS Ecole University 1963
Dr. Mathey received a doctoral degree in chemistry from the University of Paris VI in 1971. He worked for the chemical industry until 1986 and then moved to Ecole Polytechnique. He left Ecole Polytechnique for the University of California Riverside in 2003 and joined NTU in 2008. He has got several awards including the silver medal of the CNRS, the Raymond Berr – Atochem and Grignard – Wittig awards of the French Chemical Society, the Paul Langevin and Mergier – Bourdeix awards of the French Academy of Sciences, the A. von Humboldt research prize, a JSPS fellowship, the Main Group Chemistry award, and the Arbuzov prize. He is member of the French Academy of Sciences, Leopoldina Academy, Academy of Göttingen, Academia Europaea and European Academy of Sciences. He has been President of the French Chemical Society between 2000 and 2003.
Research Interests
Our research is situated at the interface between organophosphorus and transition metal chemistry. We are looking for applications in the domains of homogeneous catalysis and molecular materials. The main topics under investigation are summarized below.
Phosphorus-carbon heterocyclic chemistry
We have published more than 300 papers in this field. We can stress the following points. The 3-membered phosphirene ring has been discovered in our group. This is the most strained P-C ring with an internal angle of only 42?. We have developed the chemistry of 2H-phospholes which mimics the chemistry of cyclopentadienes. Among their various applications is the synthesis of 1-phosphanorbornadienes with a non-inversible phosphorus atom, an extremely useful feature for their use in enantioselective catalysis. A alpha-connected dimer, the so-called BIPNOR, has proven to be extremely efficient in asymmetric catalysis. No less than seven different new syntheses of phosphinines (P-analogs of pyridines) have been devised in our group. 2-Functional phosphinines and 2,2'-biphosphinines have been prepared using 2-Zr and 2-Pd derivatives. We are currently investigating the synthesis and chemistry of polyphosphorus macrocycles with inversible tri- or planar dicoordinate phosphorus atoms. Our more general aim is to pave the way for a phosphorus version of supramolecular chemistry. A book summarizing the advances in this field has been published in 2001.
Phosphorus analogues of unsaturated hydrocarbon pi-complexes
The discovery of phosphaferrocenes in our group was the starting point of the chemistry of pi-phospha-complexes. Since then, we have synthesized ?-phosphacyclopentadienyl complexes with numerous other group IV to IX transition metals. They include the paramagnetic 19-electron phosphacobaltocenes and 20-electron phosphanickelocenes. We have also extended our research to main group (Ga, Ge, Sn, Pb) derivatives. The use of phosphaferrocenes and phospharuthenocenes in asymmetric catalysis and phosphazirconocenes in polymerization catalysis is currently under active investigation in several groups. Also noteworthy is the discovery of the first eta-3-1-phosphallyl complexes (M = Fe, Co, Mo, W) which can fluctuate between eta-3 and eta-1-coordinations.
Low-coordinate phosphorus chemistry
We have started to develop the chemistry of electrophilic terminal phosphinidene complexes [RP-M(CO)5] as soon as 1982. These species behave as singlet carbenes. Another significant contribution is the synthesis of P=C double bonds from carbonyl derivatives via the phospha-Wittig reaction. We also performed the first successful epoxidations and catalytic hydrogenations of P=C double bonds. All these discoveries illustrate the diagonal carbon-phosphorus analogy. This is the theme of a book published in 1998.
Current Projects
  • Development of Novel Phosphorus Compounds and their Applications
  • Hydroxyphosphinidene: A Source of New Phosphinous Acids for Homogenous Catalyst
  • The Chemistry of Phosphorus Hectrocycles and Monovalent Phosphrous
Selected Publications
  • Wei Luo, Ana Ciric, Rongqiang Tian, Francois Mathey. (2010). The chemistry of 3-aminophospholes. Organometallics, 29, 1862-1864.
  • Ngoc Hoa Tran Huy, Bruno Donnadieu, Guy Bertrand, Francois Mathey. (2010). The phosphorus version of the oxaspiropentene-cyclobutenone rearrangement. Organometallics, 29, 1302-1304.
  • R. Tian, F. Mathey. (2010). 7-Phosphanorbornenium borohydrides: A powerful route to functional secondary phosphine-borane complexes. Organometallics, 29, 1873-1874.
  • Aholibama Escobar, Francois Mathey. (2010). Synthesis of 2,5difunctional phosphaferrocenes. Organometallics, 29, 1053-1056.
  • R. Tian, Z. Duan, X. Zhou, D. Geng, Y. Wu, F. Mathey. (2009). Phosphole-N-phenylmaleimide [4+2] cycloadducts as synthetic equivalents of nucleophilic phosphinidenes. Chemical Communications, (18), 2589-2590.

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