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1. Diruthenium aryl compounds – tuning of electrochemical responses and solubility

   https://doi.org/10.1039/D1DT03957A  

   Miller-Clark, Lyndsy A. ; Christ, Peter E. ; Ren, Tong ( January 2022 , Dalton Transactions)

   Reported herein are the two new series of diruthenium aryl compounds: Ru 2 (DiMeOap) 4 (Ar) (1a–6a) (DiMeOap = 2-(3,5-dimethoxyanilino)pyridinate) and Ru 2 ( m - i PrOap) 4 (Ar) (1b–5b) ( m - i PrOap = 2-(3-iso-propoxyanilino)pyridinate), prepared through the lithium-halogen exchange reaction with a variety of aryl halides (Ar = C 6 H 4 -4-NMe 2 (1), C 6 H 4 -4- t Bu (2), C 6 H 4 -4-OMe (3), C 6 H 3 -3,5-(OMe) 2 (4), C 6 H 4 -4-CF 3 (5), C 6 H 5 (6)). The molecular structures of these compounds were established with X-ray diffraction studies. Additionally, these compounds were characterized using electronic absorption and voltammetric techniques. Compounds 1a–6a and 1b–5b are all in the Ru 2 5+ oxidation state, with a ground state configuration of σ 2 π 4 δ 2 (π*δ*) 3 ( S = 3/2). Use of the modified ap ligands (ap′) resulted in moderate increases of product yield when compared to the unsubstituted Ru 2 (ap) 4 (Ar) (ap = 2-anilinopyridinate) series. Comparisons of the electrochemical properties of 1a–6a and 1b–5b against the Ru 2 (ap′)Cl starting material reveals the addition of the aryl ligand cathodically shifted themore »Ru 2 6+/5+ oxidation and Ru 2 5+/4+ reduction potentials. These oxidation and reductions potentials are also strongly dependent on the p -substituent of the axial aryl ligands.« less
2. Steric and electronic control of an ultrafast isomerization

   https://doi.org/10.1039/c9sc02359c  

   Porter, Tyler M. ; Ostericher, Andrew L. ; Kubiak, Clifford P. ( August 2019 , Chemical Science)

   Synthetic control of the influence of steric and electronic factors on the ultrafast (picosecond) isomerization of penta-coordinate ruthenium dithietene complexes (Ru((CF 3 ) 2 C 2 S 2 )(CO)(L) 2 , where L = a monodentate phosphine ligand) is reported. Seven new ruthenium dithietene complexes were prepared and characterized by single crystal X-ray diffraction. The complexes are all square pyramidal and differ only in the axial vs. equatorial coordination of the carbonyl ligand. Fourier Transform Infrared (FTIR) spectroscopy was used to study the ν (CO) bandshapes of the complexes in solution, and these reveal rapid exchange between two or three isomers of each complex. Isomerization is proposed to follow a Berry psuedorotation-like mechanism where a metastable, trigonal bipyramidal (TBP) intermediate is observed spectroscopically. Electronic tuning of the phosphine ligands L = PPh 3 , P(( p -Me)Ph) 3 , (( p -Cl)Ph) 3 , at constant cone angle is found to have little effect on the kinetics or thermodynamic stabilities of the axial, equatorial and TBP isomers of the differently substituted complexes. Steric tuning of the phosphine ligands over a range of phosphine cone angles (135 < θ < 165°) has a profound impact on the isomerization process, and inmore »the limit of greatest steric bulk, the axial isomer is not observable. Temperature dependence of the FTIR spectra was used to obtain the relative thermodynamic stabilities of the different isomers of each of the seven ruthenium dithietene complexes. This study details how ligand steric effects can be used to direct the solution state dynamics on the picosecond time scale of discrete isomers energetically separated by <2.2 kcal mol −1 . This work provides the most detailed description to date of ultrafast isomerization in the ground states of transition metal complexes.« less
3. Highly covalent metal–ligand π bonding in chelated bis- and tris(iminoxolene) complexes of osmium and ruthenium

   https://doi.org/10.1039/d0dt01287d  

   Gianino, Jacqueline ; Brown, Seth N. ( June 2020 , Dalton Transactions)

   The bis(aminophenol) 2,2′-biphenylbis(3,5-di- tert -butyl-2-hydroxyphenylamine) (ClipH 4 ) forms trans -(Clip)Os(py) 2 upon aerobic reaction of the ligand with {( p -cymene)OsCl 2 } 2 in the presence of pyridine and triethylamine. A more oxidized species, cis -β-(Clip)Os(OCH 2 CH 2 O), is formed from reaction of the ligand with the osmium( vi ) complex OsO(OCH 2 CH 2 O) 2 , and reacts with Me 3 SiCl to give the chloro complex cis -β-(Clip)OsCl 2 . Octahedral osmium and ruthenium tris-iminoxolene complexes are formed from the chelating ligand tris(2-(3′,5′-di- tert -butyl-2′-hydroxyphenyl)amino-4-methylphenyl)amine (MeClampH 6 ) on aerobic reaction with divalent metal precursors. The complexes’ structural and electronic features are well described using a simple bonding model that emphasizes the covalency of the π bonding between the metal and iminoxolene ligands rather than attempting to dissect the parts into discrete oxidation states. Emphasizing the continuity of bonding between disparate complexes, the structural data from a variety of Os and Ru complexes show good correlations to π bond order, and the response of the intraligand bond distances to the bond order can be analyzed to illuminate the polarity of the bonding between metal and the redox-active orbital on the iminoxolenes. The osmiummore »compounds’ π bonding orbitals are about 40% metal-centered and 60% ligand-centered, with the ruthenium compounds’ orbitals about 65% metal-centered and 35% ligand-centered.« less
4. Bonding in nitrile photo-dissociating ruthenium drug candidates—A local vibrational mode study

   https://doi.org/10.1063/5.0094567  

   McCutcheon, Margaret ; Freindorf, Marek ; Kraka, Elfi ( July 2022 , The Journal of Chemical Physics)

   In this work, we investigated bonding features of 15 ruthenium(II) nitrile complexes of the type [Ru(tpy)(L)-(CH 3 CN)] n+ , containing the tridentate tpy ligand (tpy = 2,2′:6′,2″-terpyridine) and various bidentate ancillary ligands L; 12 compounds originally synthesized by Loftus et al. [J. Phys. Chem. C 123, 10291–10299 (2019)] and three new complexes. We utilized local vibrational force constants derived from the local mode theory as a quantitative measure of bond strength complemented with the topological analysis of the electron density and the natural bond orbital analysis. Loftus et al. suggested that nitrile dissociation occurs after light induced singlet–triplet transition of the original complexes and they used as a measure of nitrile release efficiency quantum yields for ligand exchange in water. They observed larger quantum yields for complexes with smaller singlet–triplet energy gaps. The major goal of this work was to assess how the Ru–NC and Ru–L bond strengths in these 15 compounds relate to and explain the experimental data of Loftus et al., particularly focusing on the question whether there is a direct correlation between Ru–NC bond strength and measured quantum yield. Our study provides the interesting result that the compounds with the highest quantum yields also have themore »strongest Ru–NC bonds suggesting that breaking the Ru–NC bond is not the driving force for the delivery process rather than the change of the metal framework as revealed by first results of a unified reaction valley approach investigation of the mechanism. Compounds with the highest quantum yield show larger electronic structure changes upon singlet–triplet excitation, i.e., larger changes in bond strength, covalency, and difference between the singlet and triplet HOMOs, with exception of the compound 12. In summary, this work provides new insights into the interplay of local properties and experimental quantum yields forming in synergy a useful tool for fine tuning of existing and future design of new nitrile releasing ruthenium compounds. We hope that this work will bring theoretical and experimental studies closer together and serves as an incubator for future collaboration between computational chemists and their experimental colleagues.« less
5. 4,5-Diazafluorene and 9,9’-Dimethyl-4,5-Diazafluorene as Ligands Supporting Redox-Active Mn and Ru Complexes

   https://doi.org/10.3390/molecules25143189  

   Henke, Wade C. ; Hopkins, Julie A. ; Anderson, Micah L. ; Stiel, Jonah P. ; Day, Victor W. ; Blakemore, James D. ( July 2020 , Molecules)

   4,5-diazafluorene (daf) and 9,9’-dimethyl-4,5-diazafluorene (Me2daf) are structurally similar to the important ligand 2,2’-bipyridine (bpy), but significantly less is known about the redox and spectroscopic properties of metal complexes containing Me2daf as a ligand than those containing bpy. New complexes Mn(CO)3Br(daf) (2), Mn(CO)3Br(Me2daf) (3), and [Ru(Me2daf)3](PF6)2 (5) have been prepared and fully characterized to understand the influence of the Me2daf framework on their chemical and electrochemical properties. Structural data for 2, 3, and 5 from single-crystal X-ray diffraction analysis reveal a distinctive widening of the daf and Me2daf chelate angles in comparison to the analogous Mn(CO)3(bpy)Br (1) and [Ru(bpy)3]2+ (4) complexes. Electronic absorption data for these complexes confirm the electronic similarity of daf, Me2daf, and bpy, as spectra are dominated in each case by metal-to-ligand charge transfer bands in the visible region. However, the electrochemical properties of 2, 3, and 5 reveal that the redox-active Me2daf framework in 3 and 5 undergoes reduction at a slightly more negative potential than that of bpy in 1 and 4. Taken together, the results indicate that Me2daf could be useful for preparation of a variety of new redox-active compounds, as it retains the useful redox-active nature of bpy but lacks the acidic, benzylic C–Hmore »bonds that can induce secondary reactivity in complexes bearing daf.« less