Doux, Marjolaine (2005) New mixed phosphorus and sulfur ligands: coordination, catalysis and theoretical study. PhD thesis DCPH, EP - DCPH Laboratoire Heteroelements et Coordination, EP/X p.492.

Alternative Locations: http://www.imprimerie.polytechnique.fr/Theses/Files/Doux.pdf

Abstract

It is well established that phosphinines (phosphorus analogues of pyridines) are fragile ligands when used in catalytic applications at metal centres (chapter 1). To provide a more robust ligand class, we have introduced two types of mixed phosphorus-sulphur ligands based on a phosphinine skeleton. This work describes their synthesis, coordination chemistry and theoretical study.
Chapter 2 deals with the synthesis of λ4-phosphinine anions. The use of a tridentate S-P-S phosphinine to favour sigma(P)- coordination to metal centres is outlined and justified.
The following chapters describe the coordination chemistry of tridentate S-P-S phosphinine anions towards group X (Ni, Pd, Pt in chapter 3), IX (Co, Rh, Ir in chapter 4), XI (Cu, Au), VIII (Fe, Ru) and VII (Mn, Re, chapter 6) metal centres. Applications in the field of catalysis (Pd), activation of small molecules (Rh, Ir) and photochemistry (Mn) are described. Studies showing that the S-P-S anion can be described as a 6-electron anionic ligand which is electronically richer than anion Cp* are presented.
A theoretical treatment (Chapter 5) rationalizes the experimental observation that addition of small molecules such as H2, O2 and CO to S-P-S based Rh and Ir complexes occurs regiospecifically. An analogous study is presented for the addition of H2 to isoelectronic Pd and Pt complexes.
Sigma(P)-coordination of λ4-phosphinine anions is not limited to tridentate ligands and can occur with bidentate S-P ligands. The use of the resulting complexes in catalysis is described in chapter 7. Synthesis, coordination chemistry and catalytic applications of related phosphabarrelenes are also described in chapter 8.

Table of content

Chapitre 1: Introduction
Chapitre 2: Synthèse d’anions λ4-phosphinine
Chapitre 3: Complexes du groupe 10
Chapitre 4: Complexes du groupe 9
Chapitre 5: Fixation de molécules sur les métaux des groupes 9 et 10: approche théorique
Chapitre 6: Complexes des groupes 11, 8 et 7
Chapitre 7: Emploi d’un ligand bidente λ4-phosphinine
Chapitre 8: Emploi de 1-phosphabarrélène
Conclusion générale
Chapitre 9: Partie expérimentale
Chapitre 10: Annexe cristallographique

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