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D. Carmichael

CNRS researcher (CR1)
Laboratory "Hétéroéléments et Coordination"
École Polytechnique, CNRS
Route de Saclay
F-91128 Palaiseau cedex
http://www.dcph.polytechnique.fr
Tel: 44.15, E-mail

Presentation :

Duncan Carmichael took MSc and DPhil degrees in organometallic chemistry at the University of Sussex. After postdoctoral work in Palaiseau, he became a permanent member of CNRS in 1995.


Expertise and research interests:

We are a small group interested in the generation of new phosphorus compounds having unusual behaviour. The enormous number of phosphorus- containing ligands that have become available in recent years is testimony to their exceptional versatility, particularly in catalysis, where they provide very precise control over the electronic and spatial environment about metal centres.

We have a major interest in the chemistry of new phosphorus- containing compounds that contain electroactive centres, with one priority area being the chemistry of new heterometallocenes. In such compounds, the nature of the phosphorus atom can be controlled through variation of the metal centre, or through changing its charge, and over a period of time we have prepared the first phosphametallocenes 1 that contain ruthenium, cobalt, nickel etc centres. Many of these show interesting redox behaviour. Given that the architecture of these quite modular species can frequently be changed through variation of substituents about the organic periphery, they provide a potential for preparing unusual electrosensitive proligands. More recently, we have become interested in how phosphametallocenes can be incorporated into more complex structures such as tri- and tetra- phosphaporphyrinogen macrocycles 2, and the use of these species as precursors for further electroactive ligands.

As a member of the EC- funded SusPhos ITN network that promotes the responsible use of phosphorus within chemistry, we are also developing atom economical approaches to water- soluble ligands (with Magpie Polymers SA), and high- stability phosphine- based catalysts for industrial processes (with the ICIQ, Tarragona).


We are also interested in the possibility of creating novel networks through coordination chemistry. A recent synthetic program has allowed us to prepare the first electron- excessive paramagnetic phosphametallocenes (phosphacobaltocenes and phosphanickelocenes). Significant electron spin density is localised upon the phospholyl rings in these compounds and we are currently interested in the possibility that their coordination compounds may have unusual spin properties.


Keywords:

Coordination chemistry, enantioselection, catalysis, metallocenes, transition metal complexes..


Publications significatives :

  • D. Carmichael, J. Klankermayer, E. Muller, KM. Pietrusiewicz, L. Ricard, N. Seeboth, S. Sowa, M. Stankevic
    Synthesis and Evaluation of Side-Arm-Alkylated Phosphametallocene Phosphines.
    Organometallics 2011, 30, 1804.

  • Y. Cabon, D. Carmichael, L. Ricard
    Redox-fixable manipulation of planar chirality in late transition metal sandwich compounds; a 1,1 '-diphosphacobaltocene/1,1 '-diphosphacobaltocenium salt couple.
    Chem. Comm. 2011, 47, 11486.

  • D.Carmichael, A. Esacalle-Lewis, G. Frison, X-F. Le Goff and E. Muller
    Synthesis of a cobalt-phospholyl half-sandwich complex and its transformation into a phosphacobaltocene.
    Chem. Comm 2012, 48, 302.


 

 

 

 


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Laboratoire Hétéroéléments et Coordination
UMR 7653

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