Alkenylphosphines: Applications in Synthesis, Catalysis and Coordination Chemistry

Abstract

Alkenylphosphines are compounds of great interest in view of their structures. The most interesting feature is the carboncarbon double bond, which is directly linked to the phosphorus atom. Nucleophilic addition or cycloaddition reactions can take place at this unsaturation, which can also be used as a coordinating part in the presence of a metal. Thus, alkenylphosphines have found numerous applications in various fields of chemistry. They are useful intermediates in organic synthesis: numerous studies are devoted to their transformation into bidentate ligands, to their use as precursors for dendrimer and polymer chemistry or as ligand for homogeneous catalysis. Due to the presence of both the phosphorus atom and the carbon-carbon double bond, they are also of great interest in coordination chemistry and their different bonding modes have been largely documented. Moreover, after complexation to transition metal, a great amount of work has been carried out on their reactivity in cycloaddition reactions, as well as in functionalization of the carbon-carbon double bond and other miscellaneous reactions. These main applications will be reviewed hereafter.

κ3(P,C,C)-Allylphosphane Iridium(III) and Rhodium(III) Complexes: Preparation and Reactivity toward Nucleophilic Reagents

“…Allylphosphanes display a versatile behavior as ligands in coordination chemistry, mainly due to their ability to coordinate via the phosphorus atom or the phosphorus atom and the CC moiety. Furthermore, their complexation to transition metals activates the alkenyl moiety, allowing for several processes that do not occur in the absence of such a coordination: e.g., addition of nucleophilic reagents by electrophilic activation, intermolecular coupling of the alkenyl moieties via [2 + 2] cycloaddition and Diels–Alder reactions.…”

Organoruthenium Complexes Containing New Phosphorus–Carbon and Phosphorus–Carbon–Sulfur Ligands Generated in the Coordination Sphere by Nucleophilic Addition Reactions

“…Functionalized phosphanes bearing a multiple carbon–carbon bond display a versatile behavior as ligands in coordination chemistry and have been reasonably well explored to date. One key feature of these hybrid phosphane–olefin ligands is their hemilability, since they are able to easily dissociate the C–C double bond and to allow interaction between the metal center and organic substrates.…”