Research Overview

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 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-invertible phosphorus atom, an extremely useful feature for their use in enantioselective catalysis. A a-connected dimer, the so-called BIPNOR, has proven to be extremely efficient in asymmetric catalysis (world patents of Rhodia). No less than seven different new syntheses of phosphinines 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 invertible 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 numerous other pentahapto-phosphacyclopentadienyl complexes with group 4 to 9 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 our and several other groups. Also noteworthy is the discovery of the first eta3-1-phosphallyl complexes (M = Fe, Co, Mo, W) which can fluctuate between eta3 and eta1-coordinations.

Low-coordinate phosphorus chemistry

Starting in 1982, we have been developing the chemistry of electrophilic terminal phosphinidene complexes [RPM (CO)5]. These species behave as singlet carbenes (eq. 1). Another significant contribution is the synthesis of P=C double bonds from carbonyl derivatives via the phospha-Wittig reaction (eq. 2). 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.

Selected Recent Publications

C. Compain, B. Donnadieu, F. Mathey. Generation and trapping of a superelectrophilic terminal fluorophosphinidene complex. Organometallics 2006, 25, 540.

E. Deschamps, F. Mathey. 2-Bromophospholide ions: Synthesis and theoretical study. Chem. Eur. J. 2005, 11, 6829.

M. Clochard, J. Grundy, B. Donnadieu, F. Mathey. A straightforward synthesis of 3-acylphospholes. Org. Lett. 2005, 7, 4511.

C. Burney, D. Carmichael, K. Forissier, J.C. Green, F. Mathey, L. Ricard. Synthesis and properties of [NiCp*(2,5-tBu2PC4H2)], a 20-valence-electron phosphanickelocene. Chem. Eur. J. 2005, 11, 5381.

Kalinina, B. Donnadieu, F. Mathey. Reaction of terminal phosphinidene complexes with acetylenic alcohols: intramolecular hydrophosphination of a phosphirene ring. Organometallics 2005, 24, 696.

A. Germoni, B. Deschamps, L. Ricard, F. Mercier, F. Mathey. The coordination chemistry of enantiopure diimines derived from 1-phosphanorbornadiene-2-carboxaldehydes. J. Organomet. Chem. 2005, 690, 1133.

J. Grundy, F. Mathey. One-pot conversion of phospholide ions into beta-functional phosphinines. Angew. Chem. Int. Ed. 2005, 43, 1082.

F. Mathey. Transient 2H-phospholes as powerful synthetic intermediates in organophosphorus chemistry. Acc. Chem. Res. 2004, 37, 954.

F. Mathey, P. Le Floch. A theoretical study of the formation of phosphaacetylene by thermolysis of triallylphosphine. J. Org. Chem. 2004, 69, 5100.

D.G. Yakhvarov, Y.H. Budnikova, N.H. Tran Huy, L. Ricard, F. Mathey. Electrochemical decomplexation of phosphine-pentacarbonyltungsten complexes: the phosphole case. Organometallics 2004, 23, 1961.

P. Toullec, L. Ricard, F. Mathey. Electrophilic alkylation of electron-rich arenes by phosphacymantrenyl-carbenium ions. Organometallics 2003, 22, 1340-1342.

B. Deschamps, L. Ricard, F. Mathey. A new type of chelating biphospholene. Organometallics 2003, 22, 1356-1357.

P. Toullec, L. Ricard, F. Mathey. Hetero-Diels-Alder reactions of 2H-phospholes with aldehydes. J. Org. Chem. 2003, 68, 2803-2806.

F. Mathey. Phospha-organic chemistry: Panorama and perspectives. Angew. Chem. Int. Ed. 2003, 42, 1578-1604 (2003)

C. Burney, D. Carmichael, K. Forissier, J.C. Green, F. Mathey, L. Ricard. Synthesis and properties of [CoCp*(2,5-PC4tBu2H2)]: The first monophosphacobaltocene. Chem. Eur. J. 2003, 9, 2567-2573.

M. Clochard, E. Mattmann, F. Mercier, L. Ricard, F. Mathey. Phosphinites derived from the 7-phospha-norbornene skeleton: First results in Asymmetric catalysis. Org. Lett. 2003, 5, 3093-3094.

E. Mattmann, F. Mathey, A. Sevin, G. Frison. De-aromatizing phospholes. J. Org. Chem. 2002, 67, 1208-1213.

E. Mattmann, F. Mercier, L. Ricard, F. Mathey. Synthesis of new tricyclic phosphines and phosphinites by intramolecular Diels-Alder reactions of trivalent phospholes. J. Org. Chem. 2002, 67, 5422-5425.

N.H. Tran Huy, L. Ricard, F. Mathey. Stepwise building of polyphosphirene chains. Angew. Chem. Int. Ed. 2001, 40, 1253-1255.

E. Deschamps, L. Ricard, F. Mathey. Synthesis and structure of a 1,1’-diphospha[2] ferrocenophane. Organometallics 2001, 20, 1499-1500.

F. Mathey, N.H. Tran Huy, A. Marinetti. Electrophilic terminal-phosphinidene complexes: versatile phosphorus analogues of singlet carbenes. Helv. Chim. Acta 2001, 84, 2938-2957.

T. Faitg, J. Soulié, J.-Y. Lallemand, F. Mercier, F. Mathey. Asymmetric isomerisation of a cyclic diene: a comparative study of BINAP and BIPNOR-rhodium(I) catalysts. Tetrahedron 2000, 56, 101-104.

K. Forissier, L. Ricard, D. Carmichael, F. Mathey. Monophospholyl analogs of cobaltocenium, rhodocenium, and iridocenium cations. Molecular structures of [MCp*(eta5 PC4H2tBu2)]+BPh4- (M = Co, Rh). Organometallics 2000, 19, 954-956.

P. Rosa, N. Mézailles, L. Ricard, F. Mathey, P. Le Floch. Dianionic homoleptic biphosphinine complexes of group 4 metals. Angew. Chem. Int. Ed. 2000, 39, 1823-1826.

F. Eymery, P. Burattin, F. Mathey, P. Savignac. Water-soluble derivatives of furyl-phosphanes. Eur. J. Org. Chem. 2000, 2425-2431 (2000)

X. Sava, L. Ricard, F. Mathey, P. Le Floch. Octaethyldiphosphaferrocene: an efficient ligand in the palladium-catalyzed Suzuki cross-coupling reaction. Organometallics 2000, 19, 4899-4903.

S. Lelièvre, F. Mercier, L. Ricard, F. Mathey. Enantiopure 1-phosphanorbornadiene-2-carboxaldehydes. Tetrahedron: Asymmetry 2000, 11, 4601-4608.

Books

F. Mathey, A. Sevin. “Molecular Chemistry of the Transition Elements” Wiley, Chichester, 1996 “Chimie moleculaire des elements de transition: un dialogue entre theorie et experience” Les Editions de L’Ecole Polytechnique, 2000

K.B. Dillon, F. Mathey, J.F. Nixon. “Phosphorus: The Carbon Copy” Wiley, Chichester, 1998

F. Mathey (Editor) “Phosphorus-Carbon Heterocyclic Chemistry: The Rise of a New Domain” Pergamon, Oxford, 2001