New Benchmark Set of Transition-Metal Coordination Reactions for the Assessment of Density Functionals

We present the WCCR10 data set of ten ligand dissociation energies of large cationic transition metal complexes for the assessment of approximate exchange--correlation functionals. We analyze nine popular functionals, namely BP86, BP86-D3, B3LYP, B3LYP-D3, B97-D-D2, PBE, TPSS, PBE0, and TPSSh by mutual comparison and by comparison to experimental gas-phase data measured with well-known precision. The comparison of all calculated data reveals a large, system-dependent scattering of results with nonnegligible consequences for computational chemistry studies on transition metal compounds. Considering further the comparison with experiment, the non-empirical functionals PBE and TPSS turn out to be among the best functionals for our reference data set. The deviation can be lowered further by including Hartree--Fock exchange. Accordingly, PBE0 and TPSSh are the two most accurate functionals for our test set, but also these functionals exhibit deviations from experiment by up to 50 kJ/mol for individual reactions. As an important result we found no functional to be reliable for all reactions. Furthermore, for some of the ligand dissociation energies studied in this work, dispersion corrections yield results which increase the deviation from experiment. This deviation increases further if structure optimization including dispersion corrections is performed. Finally, we compare our results to other benchmark studies and highlight that the performance assessed for different density functionals depends significantly on the reference molecule set chosen.Comment: 36 pages, 7 figures, 3 table

2,2,6,6-Tetra­kis(biphenyl-2-yl)-4,4,8,8-tetra­methyl­cyclo­tetra­siloxane

The title compound, [–Si(C12H9)2OSi(CH3)2O–]2, was obtained unintentionally as the product of an attempted crystallization of caesium bis­(biphenyl-2,2′-di­yl)fluoro­silicate from dimethyl­formamide. In the crystal, the mol­ecule is located on an inversion center and the siloxane ring adopts a twist-chair conformation with the two dimethyl-substituted Si atoms lying 0.7081 (5) Å out of the plane defined by the two bis­(biphenyl-2-yl)-substituted Si atoms and the four O atoms. In each Si(C12H9)2 unit, the orientation of one terminal phenyl ring relative to the phenyl­ene ring of the other biphenyl moiety suggests a parallel displaced π–π stacking inter­action [centroid distance = 4.2377 (11) Å and dihedral angle = 15.40 (9)°]

Земля і праця його імення та життя

A crystallization-induced asymmetric transformation (CIAT) involving a radical-mediated racemization provides access to enantiopure secondary phosphine oxides. A consecutive CIAT is used to prepare enantio-and diastereo-pure tert-butyl(hydroxyalkyl)phenylphosphine oxides

A potassium tert-butoxide and hydrosilane system for ultra-deep desulfurization of fuels

Hydrodesulfurization (HDS) is the process by which sulfur-containing impurities are removed from petroleum streams, typically using a heterogeneous, sulfided transition metal catalyst under high H_2 pressures and temperatures. Although generally effective, a major obstacle that remains is the desulfurization of highly refractory sulfur-containing heterocycles, such as 4,6-dimethyldibenzothiophene (4,6-Me_2DBT), which are naturally occurring in fossil fuels. Homogeneous HDS strategies using well-defined molecular catalysts have been designed to target these recalcitrant S-heterocycles; however, the formation of stable transition metal sulfide complexes following C–S bond activation has largely prevented catalytic turnover. Here we show that a robust potassium (K) alkoxide (O)/hydrosilane (Si)-based (‘KOSi’) system efficiently desulfurizes refractory sulfur heterocycles. Subjecting sulfur-rich diesel (that is, [S] ∼ 10,000 ppm) to KOSi conditions results in a fuel with [S] ∼ 2 ppm, surpassing ambitious future governmental regulatory goals set for fuel sulfur content in all countries. Fossil fuels contain naturally occurring organosulfur impurities, with quantities varying depending on the type of feedstock. These sulfur-containing organic small molecules poison catalytic converters and generate polluting sulfur dioxides when combusted. Hydrodesulfurization (HDS) is the industrial process by which sulfur impurities are removed from petroleum fractions prior to their use as fuels. Currently, HDS is performed by treating petroleum with H_2 at high pressures and temperatures (that is, 150–2,250 psi and 400 °C) over heterogeneous catalysts such as cobalt-doped molybdenum sulfide supported on alumina (that is, CoMoS_x∕γ-Al_2O_3; Fig. 1a). However, certain organosulfur species, in particular dibenzothiophenes alkylated at positions 4 and 6, are not efficiently removed. Homogeneous strategies employing sophisticated, well-defined transition metal complexes—including those based on platinum, nickel, tungsten, molybdenum, palladium, ruthenium, rhodium, iron, cobalt, and others—have been extensively investigated. While these studies have provided valuable mechanistic insights, several fundamental issues, such as the formation of stable organometallic S–M species upon C–S bond activation by the metal centre (Fig. 1b), generally restrict industrial implementation of such methods. Rare examples of desulfurization of dibenzothiophenes alkylated at the 4 and 6 positions by homogeneous transition metal catalysis utilized either Ni compounds in combination with superstoichiometric alkyl Grignard reagents or Ni or Co phosphoranimide complexes in the presence of superstoichiometric KH. These issues pose a formidable challenge for the development of new HDS methods. Moreover, increasingly strict governmental regulations require limiting the sulfur content in diesel fuel and gasoline (in the US: typically <15 and <30 ppm, respectively) as well as other fuels, rendering the development of new powerful HDS methods a primary global concern. In 2013, Grubbs and co-workers reported the KO^tBu mediated cleavage of aryl C–O bonds in lignin models in the absence of transition metals using hydrosilanes. Careful inductively coupled plasma mass spectrometry (ICP-MS) analyses of the reagents and reaction mixtures ruled out catalysis with transition metals. We thus became interested in extending this method to sulfur heterocycles of relevance in oil and gas refining applications. Herein, we report that the robust KOtBu/silane-based (that is, KOSi) system is a powerful and effective homogeneous HDS method, which desulfurizes HDS-resistant dibenzothiophenes in good yield and reduces the sulfur content in diesel fuel to remarkably low levels (Fig. 1c)

UvA-DARE (Digital Academic Repository) The Role of Readers in Writing Development: Writing Students Bringing Their Texts to the Test

The role of readers in writing development: writing students bringing their texts to the test Published in: The Sage handbook of writing development Link to publication Citation for published version (APA): Rijlaarsdam, G., Braaksma, M., Couzijn, M., Janssen, T., Kieft, M., Raedts, M.

Targeting DNA topoisomerases or checkpoint kinases results in an overload of chaperone systems, triggering aggregation of a metastable subproteome

A loss of the checkpoint kinase ataxia telangiectasia mutated (ATM) leads to impairments in the DNA damage response, and in humans causes cerebellar neurodegeneration, and an increased risk of cancer. A loss of ATM is also associated with increased protein aggregation. The relevance and characteristics of this aggregation are still incompletely understood. Moreover, it is unclear to what extent other genotoxic conditions can trigger protein aggregation as well. Here, we show that targeting ATM, but also ATR or DNA topoisomerases, results in the widespread aggregation of a metastable, disease-associated subfraction of the proteome. Aggregation-prone model substrates, including Huntingtin exon 1 containing an expanded polyglutamine repeat, aggregate faster under these conditions. This increased aggregation results from an overload of chaperone systems, which lowers the cell-intrinsic threshold for proteins to aggregate. In line with this, we find that inhibition of the HSP70 chaperone system further exacerbates the increased protein aggregation. Moreover, we identify the molecular chaperone HSPB5 as a cell-specific suppressor of it. Our findings reveal that various genotoxic conditions trigger widespread protein aggregation in a manner that is highly reminiscent of the aggregation occurring in situations of proteotoxic stress and in proteinopathies

Strategy-focused writing instruction: just observing and reflecting on a model benefits 6th grade students

Three groups of typically-developing 6th grade students (total N = 62) each completed strategy-focused writing training. Using a combined lagged-group and cross-panel design we assessed the effectiveness of a sequence of four different instructional components: observation of and group reflection on a mastery model, direct (declarative) instruction, peer feedback and solo practice. Cumulative effects on written product and writing process were assessed at baseline and after each component. Findings supported the effectiveness of strategy-focused intervention: All three groups showed gains, relative to controls, in the quality of their written products assessed by both holistic and text-analytic measures, and a more structured and goal-focused planning processes. These effects were associated almost exclusively with the modelling and reflection component. Improved performance was sustained through other instructional components but there was no strong evidence that they provided additional benefit. This finding was replicated in all three groups, and across two different text-types

A potassium tert-butoxide and hydrosilane system for ultra-deep desulfurization of fuels

Hydrodesulfurization (HDS) is the process by which sulfur-containing impurities are removed from petroleum streams, typically using a heterogeneous, sulfided transition metal catalyst under high H_2 pressures and temperatures. Although generally effective, a major obstacle that remains is the desulfurization of highly refractory sulfur-containing heterocycles, such as 4,6-dimethyldibenzothiophene (4,6-Me_2DBT), which are naturally occurring in fossil fuels. Homogeneous HDS strategies using well-defined molecular catalysts have been designed to target these recalcitrant S-heterocycles; however, the formation of stable transition metal sulfide complexes following C–S bond activation has largely prevented catalytic turnover. Here we show that a robust potassium (K) alkoxide (O)/hydrosilane (Si)-based (‘KOSi’) system efficiently desulfurizes refractory sulfur heterocycles. Subjecting sulfur-rich diesel (that is, [S] ∼ 10,000 ppm) to KOSi conditions results in a fuel with [S] ∼ 2 ppm, surpassing ambitious future governmental regulatory goals set for fuel sulfur content in all countries. Fossil fuels contain naturally occurring organosulfur impurities, with quantities varying depending on the type of feedstock. These sulfur-containing organic small molecules poison catalytic converters and generate polluting sulfur dioxides when combusted. Hydrodesulfurization (HDS) is the industrial process by which sulfur impurities are removed from petroleum fractions prior to their use as fuels. Currently, HDS is performed by treating petroleum with H_2 at high pressures and temperatures (that is, 150–2,250 psi and 400 °C) over heterogeneous catalysts such as cobalt-doped molybdenum sulfide supported on alumina (that is, CoMoS_x∕γ-Al_2O_3; Fig. 1a). However, certain organosulfur species, in particular dibenzothiophenes alkylated at positions 4 and 6, are not efficiently removed. Homogeneous strategies employing sophisticated, well-defined transition metal complexes—including those based on platinum, nickel, tungsten, molybdenum, palladium, ruthenium, rhodium, iron, cobalt, and others—have been extensively investigated. While these studies have provided valuable mechanistic insights, several fundamental issues, such as the formation of stable organometallic S–M species upon C–S bond activation by the metal centre (Fig. 1b), generally restrict industrial implementation of such methods. Rare examples of desulfurization of dibenzothiophenes alkylated at the 4 and 6 positions by homogeneous transition metal catalysis utilized either Ni compounds in combination with superstoichiometric alkyl Grignard reagents or Ni or Co phosphoranimide complexes in the presence of superstoichiometric KH. These issues pose a formidable challenge for the development of new HDS methods. Moreover, increasingly strict governmental regulations require limiting the sulfur content in diesel fuel and gasoline (in the US: typically <15 and <30 ppm, respectively) as well as other fuels, rendering the development of new powerful HDS methods a primary global concern. In 2013, Grubbs and co-workers reported the KO^tBu mediated cleavage of aryl C–O bonds in lignin models in the absence of transition metals using hydrosilanes. Careful inductively coupled plasma mass spectrometry (ICP-MS) analyses of the reagents and reaction mixtures ruled out catalysis with transition metals. We thus became interested in extending this method to sulfur heterocycles of relevance in oil and gas refining applications. Herein, we report that the robust KOtBu/silane-based (that is, KOSi) system is a powerful and effective homogeneous HDS method, which desulfurizes HDS-resistant dibenzothiophenes in good yield and reduces the sulfur content in diesel fuel to remarkably low levels (Fig. 1c)