Synthesis of Organophosphorus Compounds via the Coordination Spheres of Transition Metals: Some Non-Classical Examples

Some nonconventional applications of transition metals in organophosphorus synthesis are presented. They include: a) the reduction-complexation of phosphine sulfides; b) various applications of complexation as a mask for the reactive phosphorus center; c) some coupling and insertion reactions of phospholes and phosphirenes; d) two examples of stereochemical control via complexation and e) the dramatic changes in the electronic structures of phosphinidenes and phosphinines upon coordination. The decomplexation techniques are also emphasized. 1. Introduction 2. Reduction-Complexation of Phosphine Sulfides 3. Masking the Phosphorus Reactive Center by Complexation 4. Coupling and Insertion Reactions Within a Coordination Sphere 5. Stereochemical Control via Complexation 6. Perturbation of the Ligand Electronic Structure Upon Coordination 7. Conclusion