Platinum(II) Phenylpyridyl Schiff Base Complexes as Latent, Photoactivated, Alkene Hydrosilylation Catalysts.

Photoactivated catalysts for the hydrosilylation of alkenes with silanes offer temporal control in manufacturing processes that require silicone curing. We report the development of a range of air-stable Pt(II) (salicylaldimine)(phenylpyridyl), [Pt(sal)(ppy)], complexes as photoinitiated hydrosilylation catalysts. Some of these catalysts show appreciable latency in thermal catalysis and can also be rapidly (10 s) activated by a LED UV-light source (365 nm), to give systems that selectively couple trimethylvinylsilane and hexamethylsiloxymethylsilane to give the linear hydrosilylation product.

lattice adaptivity triggered by solid-gas reactions of cationic group 7 pincer complexes.

The group 7 complexes [M(κ-2,6-(RPO)CHN)(CO)L][BAr] [M = Mn, R = Pr, L = THF; M = Re, R = Bu, L = vacant site] undergo solid-gas reactivity with CO to form the products of THF substitution or CO addition respectively. There is a large, local, adaptive change of [BAr] anions for M = Mn, whereas for M = Re the changes are smaller and also remote to the site of reactivity.

Dehydropolymerization of Amine-Boranes using Bis(imino)pyridine Rhodium Pre-Catalysis: σ-Amine-Borane Complexes, Nanoparticles, and Low Residual-Metal BN-Polymers that can be Chemically Repurposed.

The sigma amine-borane complexes [Rh(L1)(η :η -H B⋅NRH )][OTf] (L1=2,6-bis-[1-(2,6-diisopropylphenylimino)ethyl]pyridine, R=Me, Et, Pr) are described, alongside [Rh(L1)(NMeH )][OTf]. Using R=Me as a pre-catalyst (1 mol %) the dehydropolymerization of H B ⋅ NMeH gives [H BNMeH] selectively. Added NMeH , or the direct use of [Rh(L1)(NMeH )][OTf], is required for initiation of catalysis, which is suggested to operate through the formation of a neutral hydride complex, Rh(L1)H.