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 synthesis of a range of bis(phosphine)boronium salts is reported [(R2HP)2BH2][X] (R = Ph, (t)Bu, Cy) in which the counter anion is also varied (X(-) = Br(-), [OTf](-), [BAr(F)4](-), Ar(F) = 3,5-(CF3)2C6H3). Characterization in the solid-state by X-ray diffraction suggests there are weak hydrogen bonds between the PH units of the boronium cation and the anion (X(-) = Br(-), [OTf](-)), while solution NMR spectroscopy also reveals hydrogen bonding occurs in the order [BAr(F)4](-) < [OTf](-) < Br(-). [(Ph2HP)2BH2][BAr(F)4] reacts with RhH(PPh3)3, by elimination of H2, forming [Rh(κ(1),η-PPh2BH2·PPh2H)(PPh3)2][BAr(F)4] which shows a β-B-agostic interaction from the resulting base stabilised phosphino-borane ligand. Alternatively such ligands can be assembled directly on the metal centre by reaction of in situ generated {Rh(PPh3)3}(+) and Ph2HP·BH3 to afford [Rh(κ(1),η-PPh2BH2·PPh3)(PPh3)2][BAr(F)4], which was characterised by X-ray crystallography. Addition of H3B·PPh2H to the well-defined 16-electron "T-shaped" complex [Rh(P(i)Bu3)2(PPh3)][BAr(F)4] (characterised by X-ray crystallography) formed of a mixture of base-stabilised phosphino borane ligated complexes [Rh(κ(1),η-PR2BH2·PR3)(PR3)2][BAr(F)4] (R = (i)Bu or Ph). These last observations may lend clues to the formation of bis(phosphine)boronium salts in the catalytic dehydrocoupling reaction of phosphine boranes as mediated by Rh(I) compounds.

A revised mechanism of alkyne alkoxycarbonylation via a Pd catalyst with P,N-ligands is validated through joint DFT modeling and experiments.

Ultrafast, reversible intersystem crossing (ISC) is reported under ambient conditions for the electronic ground state of the pentacoordinate cobalt nitrosyl complexes, [CoX (NO)(PMePh ) ] (X=Cl, Br), in solution. ISCs on such short timescales are more typically observed in electronically excited states reached by absorption of ultraviolet or visible light. Singlet and triplet electron spin states of the complex, corresponding to two different isomers, are populated at room temperature, and the two isomers exchange on a timescale of a few picoseconds. Ultrafast two-dimensional infrared spectroscopy observes the change in wavenumber of the NO ligand band accompanying the isomerization and associated ISC on the (spin) adiabatic ground potential energy surface. Comparison of the dynamics of the chloro- and bromo-complexes shows that inertial effects of the ligand motion have a greater effect than spin-orbit coupling on determining the forward and reverse isomerization and ISC rates.