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Lundberg, D., Lindqvist-Reis, P., Lyczko, K., Eriksson, L. & Persson, I. (2024). Coordination chemistry effects of the space-demanding solvent molecule N,N′-dimethylpropyleneurea. Dalton Transactions, 53(4), 1817-1832
Open this publication in new window or tab >>Coordination chemistry effects of the space-demanding solvent molecule N,N′-dimethylpropyleneurea
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2024 (English)In: Dalton Transactions, ISSN 1477-9226, E-ISSN 1477-9234, Vol. 53, no 4, p. 1817-1832Article in journal (Refereed) Published
Abstract [en]

Crystallographic investigations of eight homoleptic N,N '-dimethylpropyleneurea (dmpu) coordinated metal ions in the solid state, [Mg(dmpu)(5)]I-2 (1), [Ca(dmpu)(6)]I-2 (2), [Ca(dmpu)(6)](ClO4)(2) (3), [Ca(dmpu)(6)](CF3SO3)(2) (4), [Sr(dmpu)(6)](CF3SO3)(2) (5), [Ba(dmpu)(6)](CF3SO3)(2) (6), [Sc(dmpu)(6)]I-3 (7), and [Pr(dmpu)(6)]I(I-3)(2) (8), and the complex [CoBr2(dmpu)(2)] (9) as well as the structures of the dmpu coordinated calcium, strontium, barium, scandium(III) and cobalt(II) ions and the cobalt(II) bromide complex in dmpu solution as determined by EXAFS are reported. The methyl groups in the dmpu molecule are close to the oxygen donor atom, causing steric restrictions, and making dmpu space-demanding at coordination to metal ions. The large volume required by the dmpu ligand at coordination contributes to crowdedness around the metal ion with often lower coordination numbers than for oxygen donor ligands without such steric restrictions. The crowdedness is seen in M & ctdot;H distances equal to or close to the sum of the van der Waals radii. To counteract the space-demand at coordination, the dmpu molecule has an unusual ability to increase the M-O-C bond angle to facilitate as large coordination numbers as possible. M-O-C bond angles in the range of 125-170 degrees are reported depending on the crowdedness caused by the coordination figure and the M-O bond distance. All reported structures of dmpu coordinated metal ions in both the solid state and dmpu solution are summarized to study the relationship between the M-O-C bond angle and the crowdedness around the metal ion. However, highly symmetric complexes seem to be favoured in the solid state due to favourable lattice energies. As a result, the dmpu coordinated lanthanoid(III) ions are octahedral in the solid state, while they, except lutetium, are seven-coordinate in the dmpu solution.

National Category
Inorganic Chemistry
Identifiers
urn:nbn:se:su:diva-226009 (URN)10.1039/d3dt03193d (DOI)001136000300001 ()38173416 (PubMedID)2-s2.0-85181814425 (Scopus ID)
Available from: 2024-01-31 Created: 2024-01-31 Last updated: 2024-01-31Bibliographically approved
Wang, Q., Eriksson, L. & Szabó, K. J. (2023). Catalytic Homologation-Allylboration Sequence for Diastereo- and Enantioselective Synthesis of Densely Functionalized β-Fluorohydrins with Tertiary Fluoride Stereocenters. Angewandte Chemie International Edition, 62(19), Article ID e202301481.
Open this publication in new window or tab >>Catalytic Homologation-Allylboration Sequence for Diastereo- and Enantioselective Synthesis of Densely Functionalized β-Fluorohydrins with Tertiary Fluoride Stereocenters
2023 (English)In: Angewandte Chemie International Edition, ISSN 1433-7851, E-ISSN 1521-3773, Vol. 62, no 19, article id e202301481Article in journal (Refereed) Published
Abstract [en]

Homologation of trisubstituted fluoroalkenes followed by allylboration of aldehyde, ketone and imine substrates is suitable for synthesis of β-fluorohydrin and amine products. In the presence of (R)-iodo-BINOL catalyst enantioselectivities up to 99 % can be achieved by formation of a single stereoisomer with adjacent stereocenters, of which one is a tertiary C−F center.

Keywords
Allylboration, Homologation, Tertiary Fluoride, β-Fluorohydrins
National Category
Organic Chemistry
Identifiers
urn:nbn:se:su:diva-217008 (URN)10.1002/anie.202301481 (DOI)000960379200001 ()36883800 (PubMedID)2-s2.0-85151267406 (Scopus ID)
Available from: 2023-05-23 Created: 2023-05-23 Last updated: 2023-05-23Bibliographically approved
Eriksson, L. & Widmalm, G. (2023). Crystal Structure of Methyl 3-O-α-D-Glucopyranosyl 2-Acetamido-2-Deoxy-α-D-Galactopyranoside Hydrate. Journal of Chemical Crystallography, 53(3), 400-406
Open this publication in new window or tab >>Crystal Structure of Methyl 3-O-α-D-Glucopyranosyl 2-Acetamido-2-Deoxy-α-D-Galactopyranoside Hydrate
2023 (English)In: Journal of Chemical Crystallography, ISSN 1074-1542, E-ISSN 1572-8854, Vol. 53, no 3, p. 400-406Article in journal (Refereed) Published
Abstract [en]

Methyl 3-O-α-D-glucopyranosyl 2-acetamido-2-deoxy-α-D-galactopyranoside as a monohydrate, C15H27NO11·H2O, crystallizes in space group P212121, with four molecules in the unit cell. It constitutes the methyl glycoside of the carbohydrate part of the teichoic acid type polysaccharide from Micrococcus sp. A1, in which the disaccharides are joined through phosphodiester linkages. The conformation of the disaccharide is described by the glycosidic torsion angles ϕ =  − 31° and ψ =  + 1°, and the hydroxymethyl groups of the constituent monosaccharides are present in the gg and gt conformations for the sugar residues having the gluco- and galacto-configuration, respectively. For the N-acetyl group at C2 of the galactosamine residue the torsion angle τH = 147°, i.e., the amide proton has an antiperiplanar relationship to H2 of the sugar ring. The structure shows extensive hydrogen bonding along the a-direction, including the water molecule, and forms sheets with hydrophilic interactions within the sheets as a result of hydrogen bonding between disaccharides as well as hydrophobic interactions between the sheets, in particular, amongst methyl groups of the N-acetyl group of the α-D-GalpNAc residue in the disaccharides.

Keywords
Crystal structure, Carbohydrate, Disaccharide, Hydrogen bonding, DFT
National Category
Other Chemistry Topics
Identifiers
urn:nbn:se:su:diva-216325 (URN)10.1007/s10870-023-00979-z (DOI)000947447600001 ()2-s2.0-85149721653 (Scopus ID)
Available from: 2023-04-11 Created: 2023-04-11 Last updated: 2023-10-04Bibliographically approved
Matyskin, A. V., Ebin, B., Allard, S., Torapava, N., Eriksson, L., Persson, I., . . . Ekberg, C. (2023). Disordered Crystal Structure and Anomalously High Solubility of Radium Carbonate. Inorganic Chemistry, 62(30), 12038-12049
Open this publication in new window or tab >>Disordered Crystal Structure and Anomalously High Solubility of Radium Carbonate
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2023 (English)In: Inorganic Chemistry, ISSN 0020-1669, E-ISSN 1520-510X, Vol. 62, no 30, p. 12038-12049Article in journal (Refereed) Published
Abstract [en]

XRD measurements of RaCO3 revealedthat it isnot isostructural with witherite, and direct-space ab initio modeling showed that the carbonate oxygens are highly disordered.It was found that the solubility of RaCO3 is unexpectedlyhigher than the solubility of witherite (log(10) K (sp) (0) = -7.5 and -8.56,respectively), supporting the disordered nature of RaCO3. EXAFS data revealed an ionic radius of Ra2+ of 1.55 & ANGS;. Radium is the only alkaline-earth metal which forms disorderedcrystals in its carbonate phase. Radium-226 carbonate was synthesized from radium-bariumsulfate ((Ra0.76Ba0.24SO4)-Ra-226) at room temperature and characterized by X-ray powder diffraction(XRPD) and extended X-ray absorption fine structure (EXAFS) techniques.XRPD revealed that fractional crystallization occurred and that twophases were formed the major Ra-rich phase, Ra(Ba)CO3, and a minor Ba-rich phase, Ba(Ra)CO3, crystallizingin the orthorhombic space group Pnma (no. 62) thatis isostructural with witherite (BaCO3) but with slightlylarger unit cell dimensions. Direct-space ab initio modeling shows that the carbonate oxygens in the major Ra(Ba)CO3 phase are highly disordered. The solubility of the synthesizedmajor Ra(Ba)CO3 phase was studied from under- and oversaturationat 25.1 & DEG;C as a function of ionic strength using NaCl as thesupporting electrolyte. It was found that the decimal logarithm ofthe solubility product of Ra(Ba)CO3 at zero ionic strength(log(10) K (sp) (0)) is-7.5(1) (2 & sigma;) (s = 0.05 g & BULL;L-1). This is significantly higher than the log(10) K (sp) (0) of witheriteof -8.56 (s = 0.01 g & BULL;L-1), supporting the disordered nature of the major Ra(Ba)CO3 phase. The limited co-precipitation of Ra2+ within witherite,the significantly higher solubility of pure RaCO3 comparedto witherite, and thermodynamic modeling show that the results obtainedin this work for the major Ra(Ba)CO3 phase are also applicableto pure RaCO3. The refinement of the EXAFS data revealsthat radium is coordinated by nine oxygens in a broad bond distancedistribution with a mean Ra-O bond distance of 2.885(3) & ANGS;(1 & sigma;). The Ra-O bond distance gives an ionic radius ofRa(2+) in a 9-fold coordination of 1.545(6) & ANGS; (1 & sigma;).

National Category
Inorganic Chemistry
Identifiers
urn:nbn:se:su:diva-221359 (URN)10.1021/acs.inorgchem.3c01513 (DOI)001033837300001 ()37477287 (PubMedID)2-s2.0-85166382165 (Scopus ID)
Available from: 2023-09-20 Created: 2023-09-20 Last updated: 2023-09-20Bibliographically approved
Deliaval, M., Jayarajan, R., Eriksson, L. & Szabó, K. J. (2023). Three-Component Approach to Densely Functionalized Trifluoromethyl Allenols by Asymmetric Organocatalysis. Journal of the American Chemical Society, 145(18), 10001-10006
Open this publication in new window or tab >>Three-Component Approach to Densely Functionalized Trifluoromethyl Allenols by Asymmetric Organocatalysis
2023 (English)In: Journal of the American Chemical Society, ISSN 0002-7863, E-ISSN 1520-5126, Vol. 145, no 18, p. 10001-10006Article in journal (Refereed) Published
Abstract [en]

We have developed a new three-component catalytic coupling reaction of alkynyl boronates, diazomethanes, and aliphatic/aromatic ketones in the presence of BINOL derivatives. The reaction proceeds with a remarkably high enantio- and diastereoselectivity (up to three contiguous stereocenters) affording tertiary CF3-allenols in a single operational step. The reaction proceeds under mild, neutral, metal-free conditions, which leads to a high level of functional group tolerance.

National Category
Chemical Sciences
Identifiers
urn:nbn:se:su:diva-218040 (URN)10.1021/jacs.3c02852 (DOI)000981726100001 ()37126044 (PubMedID)2-s2.0-85156156133 (Scopus ID)
Available from: 2023-07-26 Created: 2023-07-26 Last updated: 2023-10-23Bibliographically approved
Jayarajan, R., Kireilis, T., Eriksson, L. & Szabó, K. J. (2022). Asymmetric Organocatalytic Homologation: Access to Diverse Chiral Trifluoromethyl Organoboron Species. Chemistry - A European Journal, 28(58), Article ID e202202059.
Open this publication in new window or tab >>Asymmetric Organocatalytic Homologation: Access to Diverse Chiral Trifluoromethyl Organoboron Species
2022 (English)In: Chemistry - A European Journal, ISSN 0947-6539, E-ISSN 1521-3765, Vol. 28, no 58, article id e202202059Article in journal (Refereed) Published
Abstract [en]

A broad range of aliphatic, aromatic, and heterocyclic boronic acids were successfully homologated using trifluorodiazoethane in the presence of BINOL derivatives to provide the corresponding chiral trifluoromethyl containing boronic acid derivatives in high yields and excellent enantioselectivity. The in situ conversion of the chiral transient boronic acids to the corresponding alcohols or β-CF3 carboxylates are also demonstrated. 

Keywords
asymmetric homologation, enantioselective, organoboron, organocatalysis, organofluorine
National Category
Chemical Sciences
Identifiers
urn:nbn:se:su:diva-209507 (URN)10.1002/chem.202202059 (DOI)000841525500001 ()35980871 (PubMedID)2-s2.0-85135960674 (Scopus ID)
Available from: 2022-09-20 Created: 2022-09-20 Last updated: 2022-10-27Bibliographically approved
Das, B., Toledo-Carrillo, E. A., Li, L., Ye, F., Chen, J., Slabon, A., . . . Åkermark, B. (2022). Cobalt Electrocatalyst on Fluorine Doped Carbon Cloth – a Robust and Partially Regenerable Anode for Water Oxidation. ChemCatChem, 14(18), Article ID e202200538.
Open this publication in new window or tab >>Cobalt Electrocatalyst on Fluorine Doped Carbon Cloth – a Robust and Partially Regenerable Anode for Water Oxidation
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2022 (English)In: ChemCatChem, ISSN 1867-3880, E-ISSN 1867-3899, Vol. 14, no 18, article id e202200538Article in journal (Refereed) Published
Abstract [en]

The low stability of the electrocatalysts at water oxidation (WO) conditions and the use of expensive noble metals have obstructed large-scale H2 production from water. Herein, we report the electrocatalytic WO activity of a cobalt-containing, water-soluble molecular WO electrocatalyst [CoII(mcbp)(OH2)] (1) [mcbp2−=2,6-bis(1-methyl-4-(carboxylate)benzimidazol-2-yl)pyridine] in homogeneous conditions (overpotential of 510 mV at pH 7 phosphate buffer) and after anchoring it on pyridine-modified fluorine-doped carbon cloth (PFCC). The formation of cobalt phosphate was identified only after 4 h continuous oxygen evolution in homogeneous conditions. Interestingly, a significant enhancement of the stability and WO activity (current density of 5.4 mA/cm2 at 1.75 V) was observed for 1 after anchoring onto PFCC, resulting in a turnover (TO) of >3.6×103 and average TOF of 0.05 s−1 at 1.55 V (pH 7) over 20 h. A total TO of >21×103 over 8 days was calculated. The electrode allowed regeneration of∼ 85 % of the WO activity electrochemically after 36 h of continuous oxygen evolution.

Keywords
Cobalt, Water Oxidation, Regenerable, Stability, Modified carbon cloth
National Category
Chemical Sciences
Identifiers
urn:nbn:se:su:diva-209771 (URN)10.1002/cctc.202200538 (DOI)000837211400001 ()2-s2.0-85135704277 (Scopus ID)
Available from: 2022-10-10 Created: 2022-10-10 Last updated: 2022-10-31Bibliographically approved
Wang, Q., Nilsson, T., Eriksson, L. & Szabó, K. J. (2022). Sulfenofunctionalization of Chiral α-Trifluoromethyl Allylboronic Acids: Asymmetric Synthesis of SCF3, SCF2R, SCN and SAr Compounds. Angewandte Chemie International Edition, 61(46), Article ID e202210509.
Open this publication in new window or tab >>Sulfenofunctionalization of Chiral α-Trifluoromethyl Allylboronic Acids: Asymmetric Synthesis of SCF3, SCF2R, SCN and SAr Compounds
2022 (English)In: Angewandte Chemie International Edition, ISSN 1433-7851, E-ISSN 1521-3773, Vol. 61, no 46, article id e202210509Article in journal (Refereed) Published
Abstract [en]

We report herein a new method for the synthesis of densely functionalized chiral allyl SCF3, SCF2R, SCN and SAr species with a separate CF3 functionality. The synthetic approach is based on selenium-catalyzed sulfenofunctionalization of chiral α-CF3 allylboronic acids. The reactions proceeded with remarkably high stereo-, diastereo- and site-selectivity, based on the formation of a stable thiiranium ion followed by rapid deborylative ring opening. © 2022 The Authors. Angewandte Chemie International Edition published by Wiley-VCH GmbH.

Keywords
Asymmetric Synthesis, Boron, Fluorine, Lewis Base, Sulfur, Synthetic aperture radar, A-stable, Diastereoselectivities, Functionalized, Ring opening, Site selectivity, Synthetic approach, Trifluoromethyl
National Category
Organic Chemistry
Identifiers
urn:nbn:se:su:diva-211707 (URN)10.1002/anie.202210509 (DOI)36152310 (PubMedID)2-s2.0-85139816780 (Scopus ID)
Note

Export Date: 22 November 2022; Article; CODEN: ACIEF; Correspondence Address: Szabó, K.J.; Department of Organic Chemistry, Sweden; email: kalman.j.szabo@su.se

Available from: 2022-11-25 Created: 2022-11-25 Last updated: 2022-11-25Bibliographically approved
Gebresenbut, G. H., Eriksson, L., Häussermann, U., Rydh, A., Mathieu, R., Vekilova, O. Y. & Shiino, T. (2022). Superconducting YAu3Si and Antiferromagnetic GdAu3Si with an Interpenetrating Framework Structure Built from 16-Atom Polyhedra. Inorganic Chemistry, 61(10), 4322-4334
Open this publication in new window or tab >>Superconducting YAu3Si and Antiferromagnetic GdAu3Si with an Interpenetrating Framework Structure Built from 16-Atom Polyhedra
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2022 (English)In: Inorganic Chemistry, ISSN 0020-1669, E-ISSN 1520-510X, Vol. 61, no 10, p. 4322-4334Article in journal (Refereed) Published
Abstract [en]

Investigations of reaction mixtures REx(Au0.79Si0.21)100–x (RE = Y and Gd) yielded the compounds REAu3Si which adopt a new structure type, referred to as GdAu3Si structure (tP80, P42/mnmZ = 16, a = 12.8244(6)/12.7702(2) Å, and c = 9.0883(8)/9.0456(2) Å for GdAu3Si/YAu3Si, respectively). REAu3Si was afforded as millimeter-sized faceted crystal specimens from solution growth employing melts with composition RE18(Au0.79Si0.21)82. In the GdAu3Si structure, the Au and Si atoms are strictly ordered and form a framework built of corner-connected, Si-centered, trigonal prismatic units SiAu6. RE atoms distribute on 3 crystallographically different sites and each attain a 16-atom coordination by 12 Au and 4 Si atoms. These 16-atom polyhedra commonly fill the space of the unit cell. The physical properties of REAu3Si were investigated by heat capacity, electrical resistivity, and magnetometry techniques and are discussed in the light of theoretical predictions. YAu3Si exhibits superconductivity around 1 K, whereas GdAu3Si shows a complex magnetic ordering, likely related to frustrated antiferromagnets exhibiting chiral spin textures. GdAu3Si-type phases with interesting magnetic and transport properties may exist in an extended range of ternary RE–Au–Si systems, similar to the compositionally adjacent cubic 1/1 approximants RE(Au,Si)∼6.

National Category
Chemical Sciences
Identifiers
urn:nbn:se:su:diva-204400 (URN)10.1021/acs.inorgchem.1c03456 (DOI)000780256600013 ()35225597 (PubMedID)
Available from: 2022-05-06 Created: 2022-05-06 Last updated: 2022-05-06Bibliographically approved
Yang, J., Massaro, L., Krajangsri, S., Singh, T., Su, H., Silvi, E., . . . Andersson, P. G. (2021). Combined Theoretical and Experimental Studies Unravel Multiple Pathways to Convergent Asymmetric Hydrogenation of Enamides. Journal of the American Chemical Society, 143(51), 21594-21603
Open this publication in new window or tab >>Combined Theoretical and Experimental Studies Unravel Multiple Pathways to Convergent Asymmetric Hydrogenation of Enamides
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2021 (English)In: Journal of the American Chemical Society, ISSN 0002-7863, E-ISSN 1520-5126, Vol. 143, no 51, p. 21594-21603Article in journal (Refereed) Published
Abstract [en]

We present a highly efficient convergent asymmetric hydrogenation of E/Z mixtures of enamides catalyzed by N,P–iridium complexes supported by mechanistic studies. It was found that reduction of the olefinic isomers (E and Z geometries) produces chiral amides with the same absolute configuration (enantioconvergent hydrogenation). This allowed the hydrogenation of a wide range of E/Z mixtures of trisubstituted enamides with excellent enantioselectivity (up to 99% ee). A detailed mechanistic study using deuterium labeling and kinetic experiments revealed two different pathways for the observed enantioconvergence. For α-aryl enamides, fast isomerization of the double bond takes place, and the overall process results in kinetic resolution of the two isomers. For α-alkyl enamides, no double bond isomerization is detected, and competition experiments suggested that substrate chelation is responsible for the enantioconvergent stereochemical outcome. DFT calculations were performed to predict the correct absolute configuration of the products and strengthen the proposed mechanism of the iridium-catalyzed isomerization pathway.

Keywords
Mixtures, Catalysts, Isomerization, Molecular structure, Hydrogenation
National Category
Chemical Sciences
Identifiers
urn:nbn:se:su:diva-200544 (URN)10.1021/jacs.1c09573 (DOI)000732028000001 ()34905345 (PubMedID)
Available from: 2022-01-08 Created: 2022-01-08 Last updated: 2022-10-11Bibliographically approved
Organisations
Identifiers
ORCID iD: ORCID iD iconorcid.org/0000-0001-7947-3860

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