A general route for the controlled functionalization of polyferrocenylsilane‐block‐polyvinylsiloxane copolymers, which should be transferable to other silicone‐based materials, is developed utilizing the photoinitiated thiol‐ene reaction. Poly(ferrocenyldimethylsilane)54‐block‐poly(methylvinylsiloxane)510 (PFDMS54‐b‐PMVS510) is synthesized via sequential living anionic polymerization and quantitatively functionalized with a range of thiols, with the aim of tuning the solubility of the resulting materials for self‐assembly studies or incorporating more complex functionality for subsequent applications. When functionalization is attempted using a deficit of thiol, the photoinitiator 2,2‐dimethoxy‐2‐phenylacetophenone, used to accelerate the radical reaction, is found to cause significant cross‐linking of the polysiloxane chain. Reproducible percentage thiol‐ene functionalization of the polysiloxane block can be achieved by the use of PFDMS53‐b‐PMVS58/PDMS444 (PDMS = polydimethylsiloxane), prepared by the copolymerization of cyclic siloxane monomers, [Me(CHCH2)SiO]3 and [Me2SiO]3, to tune the vinyl group incorporation pre‐functionalization.

The properties of 13 monodentate P-donor ligands not previously characterized in the Ligand Knowledge Base (LKB) approach have been determined computationally, allowing NEW LIGANDS ON LKB-P PROPERTY MAP 707 their addition to the LKB-P map of ligand space. 1 Consideration of ligand positions and close neighbors in ligand space can help to establish a chemical context and hence guide their application to organometallic catalysis. Here we demonstrate this potential application of the LKB-P map and discuss known and likely applications of these ligands.