Crystal structure of N,N,N-tris-[(1,3-benzo-thia-zol-2-yl)meth-yl]amine.

The title compound, C24H18N4S3, exhibits three near planar benzo-thia-zole systems in a pseudo-C 3 conformation. The dihedral angles between the planes of the benzo-thia-zole groups range from 112.56 (4) to 124.68 (4)° In the crystal, mol-ecules are connected to each other through three short C-H⋯N contacts, forming an infinite chain along [100]. The molecules are also linked by π-π interactions with each of the three five-membered thiazole rings. [inter-centroid distance range: 3.614 (1)-4.074 (1) Å, inter-planar distance range: 3.4806 (17)-3.6902 (15) Å, slippage range: 0.759 (3)-1.887 (3) Å]

2-(Phenylsulfanyl)aniline

In the title compound, C12H11NS, the aniline and phenyl rings have a skewed conformation with a dihedral angle of 81.31 (7)°. There is a short intramolecular N–H...S contact enclosing an S(5) ring motif. In the crystal, molecules are linked via N–H...S hydrogen bonds, forming chains along [10-3]. The chains are linked via N—H...π and C—H...π interactions, forming layers parallel to plane (010). No π–π interactions are noted between the layers

Bis[μ-2-(phenylsulfanyl)anilido-κ2N:N]bis[bis(tetrahydrofuran-κO)lithium]

The title compound, [Li2(C12H10NS)2(C4H8O)4], exists as a dimer in the solid state, with a central four-membered Li2N2 ring that is planar by crystallographic inversion symmetry. The Li atoms are bridged by the N atoms of two anilide ligands, and each Li atom is coordinated by two O atoms from tetrahydrofuran ligands, resulting in a distorted tetrahedral N2O2 environment. One of the tetrahydrofuran rings is disordered over two sets of sites in a 0.665 (16):0.335 (6) ratio

Electrosynthesis of Iminophosphoranes: Accessing P(V) Ligands from P(III) Phosphines

Iminophosphorane P(V) compounds are accessed via electrochemical oxidation of commercially available P(III) ligands, including mono-, di- and tri-dentate phosphines as well as chiral phosphines. The reaction uses inexpensive bis(trimethylsilyl)carbodiimide as an efficient and safe aminating reagent. DFT calculations, cyclic voltammetry, and NMR spectroscopic studies provide insight into the reaction mechanism. The proposed mechanism based on the data reveals a special case of sequential paired electrolysis, namely a domino electrolysis process in which intermediates generated at the cathode are subsequently oxidized at the anode, followed by an additional convergent paired electrolysis process. DFT calculations of the frontier orbitals of the iminophosphorane are compared to those of the analogous P(III) phosphines and P(V) phosphine oxides. This reveals that N-cyano-iminophosphoranes have both a higher HOMO and lower LUMO than their analogous phosphine oxide, rendering them suitable for both sigma-donating and pi-back-bonding

Relevance of chemical vs electrochemical oxidation of tunable carbene iridium complexes for catalytic water oxidation

Based on previous work that identified iridium(III) Cp* complexes containing a C,N-bidentate chelating triazolylidene-pyridyl ligand (Cp* = pentamethylcyclopentadienyl, C 5Me 5 –) as efficient molecular water oxidation catalysts, a series of new complexes based on this motif has been designed and synthesized in order to improve catalytic activity. Modifications include specifically the introduction of electron-donating substituents into the pyridyl unit of the chelating ligand (H, a; 5-OMe, b; 4-OMe, c; 4-tBu, d; 4-NMe 2, e), as well as electronically active substituents on the triazolylidene C4 position (H, 8; COOEt, 9; OEt, 10; OH, 11; COOH, 12). Chemical oxidation using cerium ammonium nitrate (CAN) indicates a clear structure-activity relationship with electron-donating groups enhancing catalytic turnover frequency, especially when the donor substituent is positioned on the triazolylidene ligand fragment (TOF max = 2500 h – 1 for complex 10 with a MeO group on pyr and a OEt-substituted triazolylidene, compared to 700 h – 1 for the parent benchmark complex without substituents). Electrochemical water oxidation does not follow the same trend, and reveals that complex 8b without a substituent on the triazolylidene fragment outperforms complex 10 by a factor of 5, while in CAN-mediated chemical water oxidation, complex 10 is twice more active than 8b. This discrepancy in catalytic activity is remarkable and indicates that caution is needed when benchmarking iridium water oxidation catalysts with chemical oxidants, especially when considering that application in a potential device will most likely involve electrocatalytic water oxidation

Relevance of chemical vs electrochemical oxidation of tunable carbene iridium complexes for catalytic water oxidation

\u3cp\u3eBased on previous work that identified iridium(III) Cp* complexes containing a C,N-bidentate chelating triazolylidene-pyridyl ligand (Cp* = pentamethylcyclopentadienyl, C \u3csub\u3e5\u3c/sub\u3eMe \u3csub\u3e5\u3c/sub\u3e \u3csup\u3e–\u3c/sup\u3e) as efficient molecular water oxidation catalysts, a series of new complexes based on this motif has been designed and synthesized in order to improve catalytic activity. Modifications include specifically the introduction of electron-donating substituents into the pyridyl unit of the chelating ligand (H, a; 5-OMe, b; 4-OMe, c; 4-tBu, d; 4-NMe \u3csub\u3e2\u3c/sub\u3e, e), as well as electronically active substituents on the triazolylidene C4 position (H, 8; COOEt, 9; OEt, 10; OH, 11; COOH, 12). Chemical oxidation using cerium ammonium nitrate (CAN) indicates a clear structure-activity relationship with electron-donating groups enhancing catalytic turnover frequency, especially when the donor substituent is positioned on the triazolylidene ligand fragment (TOF \u3csub\u3emax\u3c/sub\u3e = 2500 h \u3csup\u3e–\u3c/sup\u3e \u3csup\u3e1\u3c/sup\u3e for complex 10 with a MeO group on pyr and a OEt-substituted triazolylidene, compared to 700 h \u3csup\u3e–\u3c/sup\u3e \u3csup\u3e1\u3c/sup\u3e for the parent benchmark complex without substituents). Electrochemical water oxidation does not follow the same trend, and reveals that complex 8b without a substituent on the triazolylidene fragment outperforms complex 10 by a factor of 5, while in CAN-mediated chemical water oxidation, complex 10 is twice more active than 8b. This discrepancy in catalytic activity is remarkable and indicates that caution is needed when benchmarking iridium water oxidation catalysts with chemical oxidants, especially when considering that application in a potential device will most likely involve electrocatalytic water oxidation. \u3c/p\u3

CCDC 1909357: Experimental Crystal Structure Determination

Related Article: Marta Olivares, Cornelis J. M. van der Ham, Velabo Mdluli, Markus Schmidtendorf, Helge Müller-Bunz, Tiny W.G.M Verhoeven, Mo Li, Hans J. W. Niemantsverdriet, Dennis G. H. Hetterscheid, Stefan Bernhard, Martin Albrecht, J. W. Hans Niemantsverdriet|2020|Eur.J.Inorg.Chem.|2020|801|doi:10.1002/ejic.20200009

CCDC 1909355: Experimental Crystal Structure Determination

Related Article: Marta Olivares, Cornelis J. M. van der Ham, Velabo Mdluli, Markus Schmidtendorf, Helge Müller-Bunz, Tiny W.G.M Verhoeven, Mo Li, Hans J. W. Niemantsverdriet, Dennis G. H. Hetterscheid, Stefan Bernhard, Martin Albrecht, J. W. Hans Niemantsverdriet|2020|Eur.J.Inorg.Chem.|2020|801|doi:10.1002/ejic.20200009

CCDC 1909358: Experimental Crystal Structure Determination

Related Article: Marta Olivares, Cornelis J. M. van der Ham, Velabo Mdluli, Markus Schmidtendorf, Helge Müller-Bunz, Tiny W.G.M Verhoeven, Mo Li, Hans J. W. Niemantsverdriet, Dennis G. H. Hetterscheid, Stefan Bernhard, Martin Albrecht, J. W. Hans Niemantsverdriet|2020|Eur.J.Inorg.Chem.|2020|801|doi:10.1002/ejic.20200009