Sunscreen-Assisted Selective Photochemical Transformations

In this review, we describe a simple and general procedure to accomplish selective photochemical reaction sequences for two chromophores that are responsive to similar light frequencies. The essence of the method is based on the exploitation of differences in the molar absorptivity at certain wavelengths of the photosensitive groups, which is enhanced by utilizing light-absorbing auxiliary filter molecules, or “sunscreens”. Thus, the filter molecule hinders the reaction pathway of the least absorbing molecule or group, allowing for the selective reaction of the other. The method was applied to various photochemical reactions, from photolabile protecting group removal to catalytic photoinduced olefin metathesis in different wavelengths and using different sunscreen molecules. Additionally, the sunscreens were shown to be effective also when applied externally to the reaction mixture, avoiding any potential chemical interactions between sunscreen and substrates and circumventing the need to remove the light-filtering molecules from the reaction mixture, adding to the simplicity and generality of the method

Light-induced olefin metathesis

Light activation is a most desirable property for catalysis control. Among the many catalytic processes that may be activated by light, olefin metathesis stands out as both academically motivating and practically useful. Starting from early tungsten heterogeneous photoinitiated metathesis, up to modern ruthenium methods based on complex photoisomerisation or indirect photoactivation, this survey of the relevant literature summarises past and present developments in the use of light to expedite olefin ring-closing, ring-opening polymerisation and cross-metathesis reactions

Ruthenium benzylidene and benzylidyne complexes: Alkene metathesis catalysis

editorial reviewedThis chapter surveys the various types of ruthenium benzylidene complexes that were described in the literature within the years 1995–2021. The emphasis is placed on their synthesis, characterization, and chemical reactivity rather than their catalytic activity. Some remarkable structure/activity relationships that helped tailoring the coordination sphere of the metal center through ligand design in order to achieve the highest possible activities and selectivities toward various kinds of olefin metathesis reactions are nonetheless highlighted. A brief overview of the few ruthenium benzylidyne complexes that have been reported thus far is also included

Thermal properties of ruthenium alkylidene-polymerized dicyclopentadiene

Differential scanning calorimetry (DSC) analysis of ring opening methatesis polymerization (ROMP) derived polydicyclopentadiene (PDCPD) revealed an unexpected thermal behavior. A recurring exothermic signal can be observed in the DSC analysis after an elapsed time period. This exothermic signal was found to be proportional to the resting period and was accompanied by a constant increase in the glass-transition temperature. We hypothesize that a relaxation mechanism within the cross-linked scaffold, together with a long-lived stable ruthenium alkylidene species are responsible for the observed phenomenon

Tuning the Latency by Anionic Ligand Exchange in Ruthenium Benzylidene Phosphite Complexes

Recently discovered cis-dichloro benzylidene phosphite complexes are latent catalysts at room temperature and exhibit exceptional thermal and photochemical activation behavior in olefin metathesis reactions. Most importantly, the study of these catalysts has allowed their introduction in efficient 3-D printing applications of ring-opening metathesis derived polymers and the control of chromatically orthogonal chemical processes. Moreover, their combination with plasmonic Au-nanoparticles has given rise to novel smart materials that are responsive to light. Given the importance of the ligand shell in the initiation and reactivity behavior of this family of complexes, we set out to investigate the effect of anionic ligand exchange. Thus, we report herein two new ruthenium benzylidene benzylphosphite complexes where the chloride anionic ligands have been replaced by bromide and iodide anions (cis-Ru-Phos-Br2 & cis-Ru-Phos-I2). The thermal and photochemical activations of these dormant catalysts in a variety of ring-closing and ring-opening metathesis polymerization (RCM and ROMP) reactions were thoroughly studied and compared with the previously known chloride precatalyst. Photochemical RCM studies provided similar results, especially in non-hindered reactions, with the UV-A wavelength being the best in all cases. On the other hand, the thermal activation profile exposed that the anionic ligand significantly affects reactivity. Notably, cis-Ru-Phos-I2 disclosed particularly impressive initiation efficiency compared to the other members of the family

New latent metathesis catalysts equipped with exchangeable boronic ester groups on the NHC

<p>Latent metathesis catalysts equipped with boronate esters of diols as exchangeable end-groups on their NHC ligands and an S-chelated ruthenium-benzylidene core were synthesized. The stable S-chelated ruthenium complexes underwent hydrolysis under mild acidic conditions, allowing easy exchange of terminal units by several 1,2- and 1,3-diols, without degrading the central ruthenium benzylidene. Using this strategy, we also prepared metathesis catalysts equipped with diallyl substrates at the termini that showed concentration dependency on RCM reactions. Notably, the larger dendritic catalysts were more efficient at the more dilute condition.</p

Right Answer for the Right Reason? Benchmarking Protocols and Pitfalls on a Ru-Metathesis Example

A layered meta-benchmarking analysis was devised with the aim of illustrating how to produce an experimental/computational protocol for the method selection and estimation of Gibbs energies of catalytically prominent reactions. Our test subject involved the active–latent equilibrium through the cis–trans isomerism of two metathesis catalysts: mesitylene-Ru-SCF3-Cl and diisopropylphenyl-Ru-SCF3-Cl. The strategy was two-fold: first to perform a computational benchmark for the energies in the gas phase, followed by benchmarking the enthalpy and the Gibbs energy, including solvation and entropy, from experimental references. This “wedding cake” build-up of subsequent methods applied to our particular small test reaction indicates that: (1) DLPNO-CCSD(T)/CBS works well as a reference method for large systems. (2) Among several functionals ωB97XD and M06 were the most accurate. (3) Choosing between IEF-PCM and SMD solvation models turned out to be case dependent. (4) For the vibrational entropic component, low-frequency vibrations often produce humungous errors, which can be improved by Cramer and Truhlar’s or Grimme’s methods; however, their cut-off parameters had to be lowered from their standard values. (5) Solvation methods are important for enthalpies, but they are inadequate for entropies. (6) All of these components are equally important for the accuracy of organometallic complexes’ reactions. The only way to find the right method for the right reasons is to be sure to match all of the Gibbs energy terms to benchmarked experimental and computational values

Synthesis, characterisation, electronic spectra and electrochemical investigation of ferrocenyl-terminated dendrimers

Two new dodecaferrocenyl dendrimers have been prepared using a sixfold Sonogashira coupling reaction and sixfold Huisgen cycloaddition, respectively. In addition, a dendron containing four ferrocenyl groups has been synthesised by conventional synthetic methods. Electrochemical studies have shown that all the ferrocene units are electrochemically equivalent. Moreover, when treated with acid these compounds form multicharged methylium near-infrared-absorbing dendritic dyes with a high extinction coefficient