Detailed example of the identification and crystallographic analysis of a pseudo-merohedrally twinned crystal.

A detailed description of the procedures utilized in the nonroutine X-ray single-crystal structural determination and refinement of a pseudo-merohedrally twinned crystal of an Fe/Ni organometallic complex is presented. It illustrates to the practitioners of crystallography how to properly handle such cases and describes the logic and concrete steps necessary to account for the twinning, pseudo-symmetry and atomic positional disorder

Expanding the scope of Cu(I) Catalyzed “Click Chemistry” with abnormal NHCs: three-fold click to Tris-Triazoles

Ho NKT, Reichmann SO, Rottschäfer D, Herbst-Irmer R, Ghadwal R. Expanding the scope of Cu(I) Catalyzed “Click Chemistry” with abnormal NHCs: three-fold click to Tris-Triazoles. Catalysts. 2017;7(9): 262.Cationic copper(I) complexes [Cu(aIPrPh)(IPr)]I (3) and [Cu(aIPrPh)2]I (4) featuring an abnormal N-heterocyclic carbene (aNHC) (aIPrPh = 1,3-bis(2,6-diisopropylphenyl)-2-phenyl- imidazol-4-ylidene) and/or an NHC (IPr = 1,3-Bis(2,6-diisopropylphenyl)imidazol-2-ylidene) ligand(s) are reported. Treatment of Cu(aIPrPh)I (2) with IPr affords complex 3. Reaction of (IPrPh)I (1) (IPrPh = 1,3-bis(2,6-diisopropylphenyl)-2-phenyl-imidazolium) with CuI in the presence of K{N(SiMe3)2} leads to the formation of 4. Complexes 3 and 4 represent rare examples of mixed aNHC-NHC and bis-aNHC metal complexes, respectively. They are characterized by elemental analysis, NMR spectroscopic, and mass spectrometric studies. The solid-state molecular structures of 3 and 4 have been determined by single crystal X-ray diffraction analyses. The catalytic activity of 2, 3, and 4 has been investigated in the [3+2] cycloaddition of alkynes and organic azides, affording triazole derivatives in an almost quantitative yield. Notably, complexes 2, 3, and 4 are excellent catalysts for the three-fold cycloaddition of a tris-azide with various alkynes. This catalytic protocol offers a high yield access to tris-triazoles in a shorter reaction time and considerably reduces the experimental work-up compared to the classical synthetic method

Fundamental characterization, photophysics and photocatalysis of a base metal iron(II)-cobalt(III) dyad

A new base metal iron-cobalt dyad has been obtained by connection between a heteroleptic tetra-NHC iron(II) photosensitizer combining a 2,6-bis[3-(2,6-diisopropylphenyl)imidazol-2-ylidene]pyridine with 2,6-bis(3-methyl-imidazol-2-ylidene)-4,4′-bipyridine ligand, and a cobaloxime catalyst. This novel iron(II)-cobalt(III) assembly has been extensively characterized by ground- and excited-state methods like X-ray crystallography, X-ray absorption spectroscopy, (spectro-)electrochemistry, and steady-state and time-resolved optical absorption spectroscopy, with a particular focus on the stability of the molecular assembly in solution and determination of the excited-state landscape. NMR and UV/Vis spectroscopy reveal dissociation of the dyad in acetonitrile at concentrations below 1 mM and high photostability. Transient absorption spectroscopy after excitation into the metal-to-ligand charge transfer absorption band suggests a relaxation cascade originating from hot singlet and triplet MLCT states, leading to the population of the $^{3}$MLCT state that exhibits the longest lifetime. Finally, decay into the ground state involves a $^{3}$MC state. Attachment of cobaloxime to the iron photosensitizer increases the $^{3}$MLCT lifetime at the iron centre. Together with the directing effect of the linker, this potentially makes the dyad more active in photocatalytic proton reduction experiments than the analogous two-component system, consisting of the iron photosensitizer and Co(dmgH)$_2$(py)Cl. This work thus sheds new light on the functionality of base metal dyads, which are important for more efficient and sustainable future proton reduction systems

Unusual formation of a N-heterocyclic germylene via homolytic cleavage of a C-C bond

Deutsche Forschungsgemeinschaft [RO 224/60-1]; Danish National Research Foundation [DNRF93]; Centre for Materials Crystallography; Norwegian Research Council through the CoE Centre for Theoretical and Computational Chemistry (CTCC) [179568/V30]; China Scholarship Council; Norwegian Supercomputing Program (NOTUR) [NN4654K]Reaction of the monoanionic radical salt IP center dot-K+ (IP = (Py)CH(=NR); Py = C5H4N, R = 2,6-iPr(2)C(6)H(3); alpha-iminopyridine) with GeCl2(dioxane) afforded compound (IPGeCl)(2) (1) which produced red blocks of IPGe: (2), when treated with KC8 in toluene. 1 is a digermylene formed via C-C coupling between two carbon-centered radicals. 2 can be considered as an analogue of a N-heterocyclic carbene, which exhibits a five-membered GeC2N2 ring with one CQC double bond. 2 is formed by two-electron reduction of 1 with cleavage of the two Ge-Cl bonds and the central C-C single bond

Palladium-Catalyzed Direct C2-Arylation of an N-Heterocyclic Carbene: An Atom-Economic Route to Mesoionic Carbene Ligands

Ghadwal R, Reichmann SO, Herbst-Irmer R. Palladium-Catalyzed Direct C2-Arylation of an N-Heterocyclic Carbene: An Atom-Economic Route to Mesoionic Carbene Ligands. Chemistry - A European Journal. 2015;21(11):4247-4251.Blocking the C2 position of an imidazole‐derived classical N‐heterocyclic carbene (NHC) with an aryl group is an essential strategy to establish a route to mesoionic carbenes (MICs), which coordinate to the metal via the C4 (or C5) carbon atom. An efficient catalytic route to MIC precursors by direct arylation of an NHC is reported. Treatment of 1,3‐bis(2,6‐diisopropylphenyl)imidazol‐2‐ylidene (IPr) with an aryl iodide (RC6H4I) in the presence of 0.5 mol % of [Pd2(dba)3] (dba=dibenzylideneacetone) precatalyst affords the C2‐arylated imidazolium salts {IPr(C6H4R)}I (R=H, 4‐Me, 2‐Me, 4‐OMe, 4‐COOMe) in excellent (up to 92 %) yields. Treatment of {IPr(C6H5)}I with CuI and KN(SiMe3)2 exclusively affords the MIC–copper complex [(IPrPh)CuI]

rac-1,1,4-Trimethyl-5-trimethylsilyl-1,3,3a,4,6,7,8,9-octahydro-1-silanaphtho[1,2-c]furan at 153 K

The crystal structure of rac-1,1,4-trimethyl-5-trimethylsilyl-1,3,3a,4,6,7,8,9-octahydro-1-silanaphtho[1,2-c]-furan, C17H30OSi2, has been determined at low temperature

Di-My-chloro-bis[dichlorotris(2-propanol)cerium(III)] at 153 K

The structure of di-μ-chloro-bis[dichlorotris(2-propanol)cerium(III)], [CeCl3(C3H80)3]2, is reported. The Ce atoms are bridged by two C1 atoms and so a dimer is formed

A Diaza-cyclo-tetradecadiene-Bis(pyrido-silafuran) Ring System

The crystal structure of 8,8,20,20-tetramethyl-9,21-dioxa-25,26-diaza-8,20-disilapentacyclo[16.6.1.16,13.07,11.019,23]_ hexacosa-1(25),6,11,13(26),18,23-hexaene, C24H34N2O2-Si2, has been determined at low temperature. The molecule lies on a crystallographic inversion centre

Synthesis and structural investigation of R Si (R = Me, Ph) bridged di-N-heterocyclic carbenes

Ghadwal R, Reichmann SO, Carl E, Herbst-Irmer R. Synthesis and structural investigation of R Si (R = Me, Ph) bridged di-N-heterocyclic carbenes. Dalton Trans. 2014;43(36):13704-13710.Functionalization of the C4 carbon of an imidazol-derived N-heterocyclic carbene (NHC) may allow fine-tuning of the electronic and steric properties of the C2 carbene center. A facile route to silyl-functionalized di-N-heterocyclic carbenes (Di-NHCs) is described. Treatment of the polymeric lithiated NHC, {Li(IPrH)}n (1) (Li(IPrH) = {(N-2,6-iPr2C6H3)2CHCLi}C:) with a dichlorosilane affords monomeric silyl-functionalized Di-NHCs, R2Si(IPrH)2 (R = Ph, 2; Me, 3). Interestingly, silyl-functionalized mono-NHC, Ph2(Cl)Si(IPrH) (4) with a pendant chloro-substituent can also be exclusively isolated maintaining the reactants 1 and Ph2SiCl2 ratio. NHCs 2 and 4 readily form copper complexes, Ph2Si{(IPrH)CuCl}2 (5) and Ph2(Cl)Si{(IPrH)CuCl} (6), on reaction with CuCl. Straightforward conversion of an NHC to a Di-NHC (2 or 3) via C4 functionalization is reported for the first time. Molecular structures of 2, 4, 5 and 6 have been established by single crystal X-ray diffraction studies