Investigation of Isolated IrF5 -, IrF6 - Anions and M[IrF6] (M=Na, K, Rb, Cs) Ion Pairs by Matrix-Isolation Spectroscopy and Relativistic Quantum-Chemical Calculations.

The molecular IrF5 -, IrF6 - anions and M[IrF6] (M=Na, K, Rb, Cs) ion pairs were prepared by co-deposition of laser-ablated alkali metal fluorides MF with IrF6 and isolated in solid neon or argon matrices under cryogenic conditions. The free anions were obtained as well by co-deposition of IrF6 with laser-ablated metals (Ir or Pt) as electron sources. The products were characterized in a combined analysis of matrix IR spectroscopy and electronic structure calculations using two-component quasi-relativistic DFT methods accounting for spin-orbit coupling (SOC) effects as well as multi-reference configuration-interaction (MRCI) approaches with SOC. Inclusion of SOC is crucial in the prediction of spectra and properties of IrF6 - and its alkali-metal ion pairs. The observed IR bands and the computations show that the IrF6 - anion adopts an Oh structure in a nondegenerate ground state stabilized by SOC effects, and not a distorted D4h structure in a triplet ground state as suggested by scalar-relativistic calculations. The corresponding "closed-shell" M[IrF6] ion pairs with C3v symmetry are stabilized by coordination of an alkali metal ion to three F atoms, and their structural change in the series from M=Na to Cs was proven spectroscopically. There is no evidence for the formation of IrF7, IrF7 - or M[IrF7] (M=Na, K, Rb, Cs) ion pairs in our experiments.

Spectroscopic Identification of Trifluorosilylphosphinidene and Isomeric Phosphasilene and Silicon Trifluorophosphine Complex.

The perfluorinated silylphosphinidene, F3SiP, in the triplet ground state is generated by the reaction of laser-ablated silicon atoms with PF3 in solid neon and argon matrices. The reactions proceed with the initial formation of a silicon trifluorophosphine complex, F3PSi, in the triplet ground state, and a more stable inserted phosphasilene, FPSiF2, in the singlet ground state upon deposition. The trifluorosilylphosphinidene was formed through F-migration reactions of FPSiF2 and F3PSi following a two-state mechanism under irradiation with visible light (λ = 470 nm) and full arc light (λ > 220 nm), respectively. High-level quantum-chemical methods support the identification of F3PSi, FPSiF2, and F3SiP by matrix-isolation IR spectroscopy.

Reaction Entropies in Solution from Analytical Three-Dimensional Reference Interaction Site Model Derivatives with Application to Redox and Spin-Crossover Processes.

An analytical approach to compute the excess entropy of solvation at constant pressure in three-dimensional reference interaction site model (3D-RISM) calculations is presented. It includes the changes in the macroscopic dielectric constant of the solvent upon variation of temperature and density. The approach is exact within the framework of force-field descriptions of the solute and gives reasonable results for self-consistently determined electrostatics as used in the 3D-RISM-self-consistent field approach, particularly for entropy differences. The new method is applied to simple examples of reaction entropies of iron complexes in aqueous solution, for which simple gas-phase calculations and many other approaches give unreliable estimates. For both redox half-reactions and spin-crossover processes, (semi)quantitative agreement with experimental reaction entropies can be achieved out of the box.

The Supramolecular Structural Chemistry of Pentafluorosulfanyl and Tetrafluorosulfanylene Compounds.

The analysis of crystal structures of SF5 - or SF4 -containing molecules revealed that these groups are often surrounded by hydrogen or other fluorine atoms. Even though fluorine prefers F⋅⋅⋅H over F⋅⋅⋅F contacts, the latter appeared to be important in many compounds. In a significant number of datasets, the closest F⋅⋅⋅F contacts are below 95 % of the van der Waals distance of two F atoms. Moreover, a number of repeating structural motifs formed by contacts between SF5 groups was identified, including different supramolecular dimers and infinite chains. Among SF4 -containing molecules, the study focused on SF4 Cl compounds, including the first solid-state structure analyses of these reactive species. Additionally, electrostatic potential surfaces of a series of Ph-SF5 derivatives were calculated, pointing out the substituent influence on the ability of F⋅⋅⋅X contact formation (X=F or other electronegative atom). Interaction energies were calculated for different dimeric arrangements of Ph-SF5 , which were extracted from experimental crystal structure determinations.

Enabling Cysteine-Free Native Chemical Ligation at Challenging Junctions with a Ligation Auxiliary Capable of Base Catalysis.

Ligation auxiliaries are used in chemical protein synthesis to extend the scope of native chemical ligation (NCL) beyond cysteine. However, auxiliary-mediated ligations at sterically demanding junctions have been difficult. Often the thioester intermediate formed in the thiol exchange step of NCL accumulates because the subsequent S→N acyl transfer is extremely slow. Here we introduce the 2-mercapto-2-(pyridin-2-yl)ethyl (MPyE) group as the first auxiliary designed to aid the ligation reaction by catalysis. Notably, the MPyE auxiliary provides useful rates even for junctions containing proline or a ß-branched amino acid. Quantum chemical calculations suggest that the pyridine nitrogen acts as an intramolecular base in a rate-determining proton transfer step. The auxiliary is prepared in two steps and conveniently introduced by reductive alkylation. Auxiliary cleavage is induced upon treatment with TCEP/morpholine in presence of a MnII complex as radical starter. The synthesis of a de novo designed 99mer peptide and an 80 aa long MUC1 peptide demonstrates the usefulness of the MPyE auxiliary.

Evaluation of an Efficient 3D-RISM-SCF Implementation as a Tool for Computational Spectroscopy in Solution.

The 3D-RISM-SCF solvent-model implementation of Gusarov et al. [ J. Phys. Chem. A 2006, 110, 6083-6090] in the Amsterdam density functional program has been improved and extended. In particular, an accurate yet efficient representation of the solute electrostatic potential is provided. The Coulomb-potential fitting of many DFT codes can be used advantageously in this context. The extra effort compared to a point-charge representation is small for a given SCF cycle and compensated by faster SCF convergence. This allows applications to large solutes, as demonstrated by evaluation of the solvatochromism of Reichardt's dye. In general, TDDFT applications to excitation energies in solution stand out and are highlighted. Applications to the 17O NMR chemical shifts of N-methylformamide in different solvents also demonstrate the distinct advantages of 3D-RISM over continuum solvents. Limitations are observed in this case for water solvent, where the solvent shielding is overestimated. This shortcoming applies also to the 17O gas-to-liquid shift of water, where we used localized molecular orbital analyses for a deeper understanding. For such cases of extremely strong solute-solvent interactions, couplings between solute and solvent orbitals induced by the magnetic perturbation are relevant. These clearly require a quantum-mechanical treatment of the most closely bound solvent molecules. Except for such extreme cases, 3D-RISM-SCF is very well suited to treat solvent effects on NMR parameters. More serious limitations pertain to the treatment of vibrational spectra, where the absence of the coupling between solute and solvent vibrational modes limits the accuracy of applications of 3D-RISM-SCF. The reported extended, efficient, and numerically accurate 3D-RISM-SCF implementation should provide a useful tool to study chemical and spectroscopic properties of molecules of appreciable size in a realistic solvent environment.

Rydberg electron stabilizes the charge localized state of the diamine cation.

A previous controversial discussion regarding the interpretation of Rydberg spectra of gaseous dimethylpiperazine (DMP) as showing the co-existence of a localized and delocalized mixed-valent DMP+ radical cation is revisited. Here we show by high-level quantum-chemical calculations that an apparent barrier separating localized and delocalized DMP+ minima in previous multi-reference configuration-interaction (MRCI) calculations and in some other previous computations were due to unphysical curve crossings of the reference wave functions. These discontinuities on the surface are removed in state-averaged MRCI calculations and with some other, orthogonal high-level approaches, which do not provide a barrier and thus no localized minimum. We then proceed to show that in the actually observed Rydberg state of neutral DMP the 3s-type Rydberg electron binds more strongly to a localized positive charge distribution, generating a localized DMP* Rydberg-state minimum, which is absent for the DMP+ cation. This work presents a case where interactions of a Rydberg electron with the underlying cationic core alter molecular structure in a fundamental way.

Spin-Symmetry Breaking and Hyperfine Couplings in Transition-Metal Complexes Revisited Using Density Functionals Based on the Exact-Exchange Energy Density.

A small set of mononuclear manganese complexes evaluated previously for their Mn hyperfine couplings (HFCs) has been analyzed using density functionals based on the exact-exchange energy density─in particular, the spin symmetry breaking (SSB) found previously when using hybrid functionals. Employing various strong-correlation corrected local hybrids (scLHs) and strong-correlation corrected range-separated local hybrids (scRSLHs) with or without additional corrections to their local mixing functions (LMFs) to mitigate delocalization errors (DE), the SSB and the associated dipolar HFCs of [Mn(CN)4]2-, MnO3, [Mn(CN)4N]-, and [Mn(CN)5NO]2- (the latter with cluster embedding) have been examined. Both strong-correlation (sc)-correction and DE-correction terms help to diminish SSB and correct the dipolar HFCs. The DE corrections are more effective, and the effects of the sc corrections depend on their damping factors. Interestingly, the DE-corrections reduce valence-shell spin polarization (VSSP) and thus SSB by locally enhancing exact-exchange (EXX) admixture near the metal center and thereby diminishing spin-density delocalization onto the ligand atoms. In contrast, sc corrections diminish EXX admixture locally, mostly on specific ligand atoms. This then reduces VSSP and SSB as well. The performance of scLHs and scRSLHs for the isotropic Mn HFCs has also been analyzed, with particular attention to core-shell spin-polarization contributions. Further sc-corrected functionals, such as the KP16/B13 construction and the DM21 deep-neural-network functional, have been examined.

Synthesis and structural characterization of stable coinage metal (Cu, Ag, Au) cyclopentadienyl complexes.

The electron withdrawing and oxidatively stable perfluorinated Cp* ligand [C5(CF3)5]- allowed for the isolation of rare and unusually stable coinage metal complexes [M(C5(CF3)5)(PtBu3)] (M = Cu, Ag, Au), representing the first complete and structurally comparable series of group 11 Cp coordination compounds. Full characterization and structure analysis revealed distinct and partly unknown coordination motifs with hapticities ranging from η1, η3/η1 and η3/η2 for gold, silver and copper, respectively. Quantum-chemical studies using DFT methods confirm these findings and connect them to the unique electronic structure of the given ligand system.

Spin-State Splittings in 3d Transition-Metal Complexes Revisited: Toward a Reliable Theory Benchmark.

A new composite method for the calculation of spin-crossover energies in 3d transition-metal complexes based on multireference methods is presented. The method reduces to MRCISD+Q at the complete-basis-set (CBS) level for atomic ions, for which it gives excitation energies with a mean absolute error of only ca. 0.01 eV. For molecular complexes, the CASPT2+δMRCI composite approach corresponds to a CASPT2/CBS calculation augmented by a high-level MRCISD+Q-CASPT2 correction with a smaller ligand basis set. For a set of [Fe(He)6]n+ test complexes, the approach reproduces full MRCISD+Q/CBS results to within better than 0.04 eV, without depending on any arbitrary IPEA shifts. The high-quality CASPT2+δMRCI method has then been applied to a series of 3d transition-metal hexaqua complexes in aqueous solution, augmented by an elaborate 3D-RISM-SCF solvent treatment of the underlying structures. It provides unprecedented agreement with experiment for the lowest-lying vertical spin-flip excitation energies, except for the Fe3+ system. Closer examination of the latter case provides strong evidence that the observed lowest-energy excitation at 1.56 eV, which has been used frequently for evaluating quantum-chemical methods, does not arise from the iron(III) hexaqua complex in solution, but from its singly deprotonated counterpart, [Fe(H2O)5OH]2+.

Persilylation of ferrocene: the ultimate discipline in sterically overcrowded metal complexes.

We report the preparation and structural characterization of the first persilylated metallocene via the metalation of decabromoferrocene. Although Grignard conditions turned out to be insufficient due to the steric and electronic effects of silyl groups causing a decreased nucleophilicity of the metalated intermediates, stepwise lithium-halogen exchange yields complex mixtures of polysilylated compounds FeC10DMSnH10-n (n = 10, 9, 8) including the targeted decasilylated ferrocene. These mixtures were successfully separated allowing a systematic study of silylation effects on ferrocene by XRD, CV, NMR and UV/vis spectroscopy supported by DFT calculations. The findings were used to develop a high-yielding and simple preparation method to generate a tenfold substituted overcrowded ferrocene, FeC10DMS8Me2.

Spin-State Splittings in 3d Transition-Metal Complexes Revisited: Benchmarking Approximate Methods for Adiabatic Spin-State Energy Differences in Fe(II) Complexes.

The CASPT2+δMRCI composite approach reported in a companion paper has been extended and used to provide high-quality reference data for a series of adiabatic spin gaps (defined as ΔE = Equintet - Esinglet) of [FeIIL6]2+ complexes (L = CNH, CO, NCH, NH3, H2O), either at nonrelativistic level or including scalar relativistic effects. These highly accurate data have been used to evaluate the performance of various more approximate methods. Coupled-cluster theory with singles, doubles, and perturbative triples, CCSD(T), is found to agree well with the new reference data for Werner-type complexes but exhibits larger underestimates by up to 70 kJ/mol for the π-acceptor ligands, due to appreciable static correlation in the low-spin states of these systems. Widely used domain-based local CCSD(T) calculations, DLPNO-CCSD(T), are shown to depend very sensitively on the cutoff values used to construct the localized domains, and standard values are not sufficient. A large number of density functional approximations have been evaluated against the new reference data. The B2PLYP double hybrid gives the smallest deviations, but several functionals from different rungs of the usual ladder hierarchy give mean absolute deviations below 20 kJ/mol. This includes the B97-D semilocal functional, the PBE0* global hybrid with 15% exact-exchange admixture, as well as the local hybrids LH07s-SVWN and LH07t-SVWN. Several further functionals achieve mean absolute errors below 30 kJ/mol (M06L-D4, SSB-D, B97-1-D4, LC-ωPBE-D4, LH12ct-SsirPW92-D4, LH12ct-SsifPW92-D4, LH14t-calPBE-D4, LHJ-HFcal-D4, and several further double hybrids) and thereby also still overall outperform CCSD(T) or uncorrected CASPT2. While exact-exchange admixture is a crucial factor in favoring high-spin states, the present evaluations confirm that other aspects can be important as well. A number of the better-performing functionals underestimate the spin gaps for the π-acceptor ligands but overestimate them for L = NH3, H2O. In contrast to a previous suggestion, non-self-consistent density functional theory (DFT) computations on top of Hartree-Fock orbitals are not a promising path to produce accurate spin gaps in such complexes.

Solving the Azobenzene Entropy Puzzle: Direct Evidence for Multi-State Reactivity.

A solution to the azobenzene "entropy puzzle" [ J. Phys.: Condens. Matter, 2017, 29, 314002] is provided. Previous computational studies of the thermal Z → E (back-)isomerization of azobenzene could not describe the experimentally observed large negative activation entropies. Here it is shown that the experimental results are only compatible with a more complicated multistate rotation mechanism that involves a triplet excited state. Using nonadiabatic transition state theory, close to perfect agreement is achieved between all calculated and experimental Eyring parameters. We also provide new experiments that indicate the presence of a noticeable external heavy-atom effect, which is a direct result of spin-orbit coupling effects being important in the proposed mechanism. These results suggest a reexamination of the mechanisms of related thermal double bond isomerizations in other systems in cases when an excited state of triplet (or other) multiplicity becomes thermally accessible during a rotation process.

Unusually Large Effects of Charge-assisted C-H⋠⋠⋠F Hydrogen Bonds to Anionic Fluorine in Organic Solvents: Computational Study of 19 F NMR Shifts versus Thermochemistry.

A comparison of computed 19 F NMR chemical shifts and experiment provides evidence for large specific solvent effects for fluoride-type anions interacting with the σ*(C-H) orbitals in organic solvents like MeCN or CH2 Cl2 . We show this for systems ranging from the fluoride ion and the bifluoride ion [FHF]- to polyhalogen anions [ClFx ]- . Discrepancies between computed and experimental shifts when using continuum solvent models like COSMO or force-field-based descriptions like the 3D-RISM-SCF model show specific orbital interactions that require a quantum-mechanical treatment of the solvent molecules. This is confirmed by orbital analyses of the shielding constants, while less negatively charged fluorine atoms (e. g., in [EF4 ]- ) do not require such quantum-mechanical treatments to achieve reasonable accuracy. The larger 19 F solvent shift of fluoride in MeCN compared to water is due to the larger coordination number in the former. These observations are due to unusually strong charge-assisted C-H⋅⋅⋅F- hydrogen bonds, which manifest beyond some threshold negative natural charge on fluorine of ca. < -0.6 e. The interactions are accompanied by sizable free energies of solvation, in the order F- ≫[FHF]- >[ClF2 ]- >[ClF4 ]- . COSMO-RS solvation free energies tend to moderately underestimate those from the micro-solvated cluster treatment. Red-shifted and intense vibrational C-H stretching bands, potentially accessible in bulk solution, are further spectroscopic finger prints.

Fluorinated click-derived tripodal ligands drive spin crossover in both iron(II) and cobalt(II) complexes.

Control of the spin state of metal complexes is important because it leads to a precise control over the physical properties and the chemical reactivity of the metal complexes. Currently, controlling the spin state in metal complexes is challenging because a precise control of the properties of the secondary coordination sphere is often difficult. It has been shown that non-covalent interactions in the secondary coordination sphere of transition metal complexes can enable spin state control. Here we exploit this strategy for fluorinated triazole ligands and present mononuclear CoII and FeII complexes with "click"-derived tripodal ligands that contain mono-fluorinated benzyl substituents on the backbone. Structural characterization of 1 and 2 at 100 K revealed Co-N bond lengths that are typical of high spin (HS) CoII complexes. In contrast, the Fe-N bond lengths for 3 are characteristic of a low spin (LS) FeII state. All complexes show an intramolecular face-to-face non-covalent interaction between two arms of the ligand. The influence of the substituents and of their geometric structure on the spin state of the metal center was investigated through SQUID magnetometry, which revealed spin crossover occurring in compounds 1 and 3. EPR spectroscopy sheds further light on the electronic structures of 1 and 2 in their low- and high-spin states. Quantum-chemical calculations of the fluorobenzene molecule were performed to obtain insight into the influence of fluorine-specific interactions. Interestingly, this work shows that the same fluorinated tripodal ligands induce SCO behavior in both FeII and CoII complexes.

Orthogonal coiled coils enable rapid covalent labelling of two distinct membrane proteins with peptide nucleic acid barcodes.

Templated chemistry offers the prospect of addressing specificity challenges occurring in bioconjugation reactions. Here, we show two peptide-templated amide-bond forming reactions that enable the concurrent labelling of two different membrane proteins with two different peptide nucleic acid (PNA) barcodes. The reaction system is based on the mutually selective coiled coil interaction between two thioester-linked PNA-peptide conjugates and two cysteine peptides serving as genetically encoded peptide tags. Orthogonal coiled coil templated covalent labelling is highly specific, quantitative and proceeds within a minute. To demonstrate the usefulness, we evaluated receptor internalisation of two membranous receptors EGFR (epidermal growth factor) and ErbB2 (epidermal growth factor receptor 2) by first staining PNA-tagged proteins with fluorophore-DNA conjugates and then erasing signals from non-internalized receptors via toehold-mediated strand displacement.

Spin-state control of cobalt(II) and iron(II) complexes with click-derived tripodal ligands through non-covalent and fluorine-specific interactions.

The fine-tuning of intermolecular or intramolecular non-covalent interactions (NCIs) and thus the precise synthesis of metal complexes in which the spin states can be controlled by NCIs remains challenging, even though several such complexes have been intensively studied. In this regard, we present mononuclear cobalt(II) and iron(II) complexes with "click"-derived tripodal ligands that contain fluorinated benzyl substituents in the secondary coordination sphere. The complexes were co-crystallized with different solvent molecules to decipher the effect of the crystallized solvents on NCIs, and on the spin state of the metal ion. Additionally, the fluorine-specific interactions in the secondary coordination sphere were examined. We present a first structure-property correlation between the nature of interaction of the (per)fluorinated aromatic substituents on the ligand periphery, and the spin state of the metal complexes. In particular, the TF5TA containing ligand show interesting stacking motifs depending on the used solvent, and these interactions have an influence on the spin state of the cobalt(II) complexes. Furthermore, the iron(II) complex thereof, Fe(TF5TA)2(BF4)2·2EtOH displays spin crossover (SCO).

Novel synthetic pathway for the production of phosgene.

Chloride ions are efficient catalysts for the synthesis of phosgene from carbon monoxide and elemental chlorine at room temperature and atmospheric pressure. Control experiments rule out a radical mechanism and highlight the role of triethylmethylammonium trichloride, [NEt3Me][Cl3], as active species. In the catalytic reaction, commercially available [NEt3Me]Cl reacts with Cl2 to form [NEt3Me][Cl3], enabling the insertion of CO into an activated Cl─Cl bond with a calculated energy barrier of 56.9 to 77.6 kJ mol−1. As [NEt3Me]Cl is also a useful chlorine storage medium, it could serve as a catalyst for phosgene production and as chlorine storage in a combined industrial process.

Thermochemistry of FeOmHnz Species: Assessment of Some DFT Functionals.

Thermochemical data for 20 anionic, cationic, and neutral gas-phase species, including Fe0/+, FeO-/0/+/2+, FeOH0/+/2+, FeO2-/0/+, OFeOH0/+, Fe(OH)20/+, Fe(H2O)+/2+, and Fe(H2O)2+/2+ with oxidation states between +I and +IV for Fe and -I and -II for O, compiled by Schröder [ J. Phys. Chem. A 2008, 112, 13215], are used to assess the performance of the "Jacob's ladder" functionals PBE, TPSS, PBE0, and TPSSh for the SVP, TZVP, and QZVP basis sets. In addition, the BP86 and B3LYP functionals are considered. The TPSSh functional performs best. With the TZVP basis set (recommended), the mean absolute and the maximum errors are 24 and 63 kJ/mol, respectively. With 32 and 78 kJ/mol, respectively, BP86 is second best, better than PBE.