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1. Insights into the charge-transfer character of electronic transitions in ^R Cp ₂ Ti(C ₂ Fc) ₂ complexes using solvatochromism, resonance Raman spectroscopy, and TDDFT

   https://doi.org/10.1039/d0dt04282j  

   Carlton, Elizabeth S.; Sutton, Joshua J.; Gale, Ariel G.; Shields, George C.; Gordon, Keith C.; Wagenknecht, Paul S. (February 2021, Dalton Transactions)

   null (Ed.)

   A series of complexes with low-energy Fe II to Ti IV metal-to-metal charge-transfer (MMCT) transitions, Cp 2 Ti(C 2 Fc) 2 , Cp* 2 Ti(C 2 Fc) 2 , and MeOOC Cp 2 Ti(C 2 Fc) 2 , was investigated using solvatochromism and resonance Raman spectroscopy (RRS) augmented with time-dependent density functional theory (TDDFT) calculations in order to interrogate the nature of the CT transitions. Computational models were benchmarked against the experimental UV-Vis spectra and B3LYP/6-31G(d) was found to most faithfully represent the spectra. The energy of the MMCT transition was measured in 15 different solvents and a multivariate fit to the Catalán solvent parameters – solvent polarizability (SP), solvent dipolarity (SdP), solvent basicity (SB), and solvent acidity (SA) – was performed. The effect of SP indicates a greater degree of electron delocalization in the excited state (ES) than the ground state (GS). The small negative solvatochromism with respect to SdP indicates a smaller dipole moment in the ES than the GS. The effect of SB is consistent with charge-transfer to Ti. Upon excitation into the MMCT absorption band, the RRS data show enhancement of the alkyne stretching modes and of the out-of-plane bending modes of the cyclopentadienyl ring connected to Fe and the alkyne bridge. This is consistent with changes in the oxidation states of Ti and Fe, respectively. The higher-energy transitions (350–450 nm) show enhancement of vibrational modes consistent with ethnylcyclopentadienyl to Ti ligand-to-metal charge transfer (LMCT). The RRS data is consistent with the TDDFT predicted character of these transitions. TDDFT suggests that the lowest-energy transition in Cp 2 Ti(C 2 Fc) 2 CuI, where CuI is coordinated between the alkynes, retains its Fe II to Ti IV MMCT character, in agreement with the RRS data, but that the lowest-energy transitions have significant CuI to Ti character. For Cp 2 Ti(C 2 Fc) 2 CuI, excitation into the low-energy MMCT absorption band results in selective enhancement of the symmetric alkynyl stretching mode. 

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2. Probing the He  ii re-Ionization ERa via Absorbing C  iv Historical Yield (HIERACHY) I: A strong outflow from a z  ∼ 4.7 quasar

   https://doi.org/10.1093/mnras/stab1614  

   Yu, Xiaodi; Li, Jiang-Tao; Qu, Zhijie; Roederer, Ian U; Bregman, Joel N; Fan, Xiaohui; Fang, Taotao; Johnson, Sean D; Wang, Feige; Yang, Jinyi (June 2021, Monthly Notices of the Royal Astronomical Society)

   null (Ed.)

   ABSTRACT Outflows from supermassive black holes (SMBHs) play an important role in the co-evolution of themselves, their host galaxies, and the larger scale environments. Such outflows are often characterized by emission and absorption lines in various bands and in a wide velocity range blueshifted from the systematic redshift of the host quasar. In this paper, we report a strong broad line region (BLR) outflow from the z ≈ 4.7 quasar BR 1202-0725 based on the high-resolution optical spectrum taken with the Magellan Inamori Kyocera Echelle (MIKE) spectrograph installed on the 6.5 m Magellan/Clay telescope, obtained from the ‘Probing the He ii re-Ionization ERa via Absorbing C iv Historical Yield’ (HIERACHY) project. This rest-frame ultraviolet (UV) spectrum is characterized by a few significantly blueshifted broad emission lines from high ions; the most significant one is the C iv line at a velocity of $$\sim -6500$$ km s−1 relative to the H α emission line, which is among the highest velocity BLR outflows in observed quasars at z > 4. The measured properties of UV emission lines from different ions, except for O i and Ly α, also follow a clear trend that higher ions tend to be broader and outflow at higher average velocities. There are multiple C iv and Si iv absorbing components identified on the blue wings of the corresponding emission lines, which may be produced by either the outflow or the intervening absorbers. 

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3. Octahedral iron( iv )–tosylimido complexes exhibiting single electron-oxidation reactivity

   https://doi.org/10.1039/C9SC02526J  

   Sabenya, Gerard; Gamba, Ilaria; Gómez, Laura; Clémancey, Martin; Frisch, Jonathan R.; Klinker, Eric J.; Blondin, Geneviève; Torelli, Stéphane; Que, Lawrence; Martin-Diaconescu, Vlad; et al (October 2019, Chemical Science)

   High valent iron species are very reactive molecules involved in oxidation reactions of relevance to biology and chemical synthesis. Herein we describe iron( iv )–tosylimido complexes [Fe IV (NTs)(MePy 2 tacn)](OTf) 2 ( 1(IV)NTs ) and [Fe IV (NTs)(Me 2 (CHPy 2 )tacn)](OTf) 2 ( 2(IV)NTs ), (MePy 2 tacn = N -methyl- N , N -bis(2-picolyl)-1,4,7-triazacyclononane, and Me 2 (CHPy 2 )tacn = 1-(di(2-pyridyl)methyl)-4,7-dimethyl-1,4,7-triazacyclononane, Ts = Tosyl). 1(IV)NTs and 2(IV)NTs are rare examples of octahedral iron( iv )–imido complexes and are isoelectronic analogues of the recently described iron( iv )–oxo complexes [Fe IV (O)(L)] 2+ (L = MePy 2 tacn and Me 2 (CHPy 2 )tacn, respectively). 1(IV)NTs and 2(IV)NTs are metastable and have been spectroscopically characterized by HR-MS, UV-vis, 1 H-NMR, resonance Raman, Mössbauer, and X-ray absorption (XAS) spectroscopy as well as by DFT computational methods. Ferric complexes [Fe III (HNTs)(L)] 2+ , 1(III)–NHTs (L = MePy 2 tacn) and 2(III)–NHTs (L = Me 2 (CHPy 2 )tacn) have been isolated after the decay of 1(IV)NTs and 2(IV)NTs in solution, spectroscopically characterized, and the molecular structure of [Fe III (HNTs)(MePy 2 tacn)](SbF 6 ) 2 determined by single crystal X-ray diffraction. Reaction of 1(IV)NTs and 2(IV)NTs with different p -substituted thioanisoles results in the transfer of the tosylimido moiety to the sulphur atom producing sulfilimine products. In these reactions, 1(IV)NTs and 2(IV)NTs behave as single electron oxidants and Hammett analyses of reaction rates evidence that tosylimido transfer is more sensitive than oxo transfer to charge effects. In addition, reaction of 1(IV)NTs and 2(IV)NTs with hydrocarbons containing weak C–H bonds results in the formation of 1(III)–NHTs and 2(III)–NHTs respectively, along with the oxidized substrate. Kinetic analyses indicate that reactions proceed via a mechanistically unusual HAT reaction, where an association complex precedes hydrogen abstraction. 

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4. Isopropyl 3-deoxy-α- D - ribo -hexopyranoside (isopropyl 3-deoxy-α- D -glucopyranoside): evaluating trends in structural parameters

   https://doi.org/10.1107/S205322962100749X  

   Lin, Jieye; Oliver, Allen G.; Meredith, Reagan J.; Carmichael, Ian; Serianni, Anthony S. (August 2021, Acta Crystallographica Section C Structural Chemistry)

   Isopropyl 3-deoxy-α-D- ribo -hexopyranoside (isopropyl 3-deoxy-α-D-glucopyranoside), C 9 H 18 O 5 , (I), crystallizes from a methanol–ethyl acetate solvent mixture at room temperature in a 4 C 1 chair conformation that is slightly distorted towards the C5 S C1 twist-boat form. A comparison of the structural parameters in (I), methyl α-D-glucopyranoside, (II), α-D-glucopyranosyl-(1→4)-D-glucitol (maltitol), (III), and 3-deoxy-α-D- ribo -hexopyranose (3-deoxy-α-D-glucopyranose), (IV), shows that most endocyclic and exocyclic bond lengths, valence bond angles and torsion angles in the aldohexopyranosyl rings are more affected by anomeric configuration, aglycone structure and/or the conformation of exocyclic substituents, such as hydroxymethyl groups, than by monodeoxygenation at C3. The structural effects observed in the crystal structures of (I)–(IV) were confirmed though density functional theory (DFT) calculations in computed structures (I) c –(IV) c . Exocyclic hydroxymethyl groups adopt the gauche – gauche ( gg ) conformation (H5 anti to O6) in (I) and (III), and the gauche – trans ( gt ) conformation (C4 anti to O6) in (II) and (IV). The O -glycoside linkage conformations in (I) and (III) resemble those observed in disaccharides containing β-(1→4) linkages. 

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5. Conformational disorder in the crystal structure of methyl 2-acetamido-2-deoxy-β- D -glucopyranosyl-(1→4)–2-acetamido-2-deoxy-β- D -glucopyranoside (methyl β-chitobioside) methanol monosolvate

   https://doi.org/10.1107/S2053229624005199  

   Shit, Pradip; Tetrault, Timothy; Zhang, Wenhui; Yoon, Mi-Kyung; Oliver, Allen G; Serianni, Anthony S (July 2024, Acta Crystallographica Section C Structural Chemistry)

   Methyl 2-acetamido-2-deoxy-β-D-glucopyranosyl-(1→4)-2-acetamido-2-deoxy-β-D-glucopyranoside (methyl β-chitobioside), (IV), crystallizes from aqueous methanol at room temperature to give a structure (C₁₇H₃₀N₂O₂₂·CH₃OH) containing conformational disorder in the exocyclic hydroxymethyl group of one of its βGlcNAc residues. As observed in other X-ray structures of disaccharides containing β-(1→4)O-glycosidic linkages, inter-residue hydrogen bonding between O3H of the βGlcNAc bearing the OCH₃aglycone and O5 of the adjacent βGlcNAc is observed based on the 2.79 Å internuclear distance between the O atoms. The structure of (IV) was compared to that determined previously for 2-acetamido-2-deoxy-β-D-glucopyranosyl-(1→4)-2-acetamido-2-deoxy-β-D-glucopyranose (β-chitobiose), (III). TheO-glycosidic linkage torsion angles,phi(ϕ) andpsi(ψ), in (III) and (IV) differ by 6–8°. TheN-acetyl side chain conformation in (III) and (IV) shows some context dependence, with the C1—C2—N—C_cartorsion angle 10–15° smaller for the βGlcNAc residue involved in the internalO-glycosidic linkage. In (IV), conformational disorder is observed in the exocyclic hydroxymethyl (–CH₂OH) group in the βGlcNAc residue bearing the OCH₃aglycone, and a fitting of the electron density indicates an approximate 50:50 distribution of thegauche–gauche(gg) andgauche–trans(gt) conformers in the lattice. Similar behavior is not observed in (III), presumably due to the different packing structure in the vicinity of the –CH₂OH substituent that affects its ability to hydrogen bond to proximal donors/acceptors. Unlike (IV), a re-examination of the previously reported electron density of (III) revealed conformational disorder in theN-acetyl side chain attached to the reducing-end βGlcNAc residue caused by rotation about the C2—N bond. 

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