The current work reports the facile synthesis and characterization of half-sandwich compounds [Ti(η5-C9H7)(Cl)2(OR)] (3) (R = iPr (3a); R = tBu (3b); R = 2,6-Ph2C6H3 (3c); CH2CH2(CC4H3S) (3d) (prepared via treatment of Ti(η5-C9H7)Cl3 (1) with LiOR (2a, R = iC3H7; 2b, R = tC4H9; 2c, R = 2,6-Ph2C6H3; 2d, R = CH2CH2(CC4H3S)) in a 1:1 molar ratio. Additionally, compounds 3a, 3b, and 3d were also obtained when compound 1 was reacted with HOR (2a, R = iC3H7; 2b, R = tC4H9; 2d, R = CH2CH2(CC4H3S)) under reflux in benzene. The half-sandwich titanium compounds 3a–d were characterized by elemental analyses, FT-IR, and 1H and 13C1H-NMR spectroscopy. Density functional theory (DFT) calculations at the B3LYP/6-31G(d) + LANL2DZ level of theory were carried out for 1 and 3a–d in order to better understand and rationalize the nature of bonding and thus demonstrate the effect of different substituents on the structural and electronic properties. The studies confirm a similar complexation pattern despite the different chemical nature of the substituents. However, the HOMO–LUMO frontier molecular orbitals analysis revealed ligand–metal charge transfer, and the calculations predicted smaller HOMO–LUMO energy gaps for 3c.

Indenyl-titanium trichloride complexes of type [Ti{eta 5 -1-(SiMe 3 )-3-(R)-C 9 H 5 }Cl 3 ] (R = SiMe 3 ( 3a ); R = t Bu ( 3b )) were obtained by treatment of Li[1-(SiMe 3 )-3-(R)-C 9 H 5 ] (R = SiMe 3 ( 1a ); R = t Bu ( 1b )) with titanium tetrachloride ( 2 ) in a 1:1 molar ratio in the presence of isopropanol and SOCl 2 . Compounds [Ti{eta 5 -1-(SiMe 3 )-3-(R)- C 9 H 5 }Cl 2 (OEt)] (R = SiMe 3 ( 4a ); R = t Bu ( 4b )) are accessible by reacting 1a,b (R = SiMe 3 ( 1a ); R = t Bu ( 1b )) with TiCl 4 ( 2 ) in the presence of ethanol and SOCl 2 , or when 3a,b were treated with equimolar amounts of EtOH in refluxing benzene. Spectroscopic methods and single crystal X-ray diffraction analysis confirmed the pianostool geometry of 3a and 4b in the solid state. Hirshfeld surface analysis using 2D fingerprint plots of 3a and 4b were conducted to elaborate non-covalent, intermolecular interactions existing in the solid state, which accounted for the strengthening of the crystal lattice. The molecular structures of the 3 and 4 were further investigated by quantum-chemical calculations. The geometries of the compounds were optimized at the B3LYP/ 6-31G(d)+LANL2DZ level of theory, and their related molecular parameters including frontier orbital energy gap and molecular electrostatic surface potential have also been calculated to better understand their properties.

The electronic effects electron donating and withdrawing groups R on the properties of N-(4-R-phenyl)-N'-(4-nitrophenyl)oxamito zincate(II) complexes was investigated featuring R = Me (a), H (b), F (c), Cl (d) and Br (e). The N-(4-R-phenyl)-N'-(4-nitrophenyl)oxamide ligands 2 were synthesized by reacting ethyl 4-nitrooxanilate with the respective 4-substituted anilines. Subsequent treatment with [nBu4N]OH and [Zn(OAc)2(H2O)2] gave the respective zincate complexes [nBu4N]2[Zn(N-(4-nitrophenyl)-N'-(4-substituted phenyl)oxamides)2] (3). Spectroscopic methods were used to describe compounds 2a–e and 3a–e. Single crystal X-ray diffraction analysis confirmed the formation of 3a–c in the solid state. The tetrahedral coordination sphere of the zinc (II) ion features four amide nitrogen donor atoms based on two ethanediamide ligands. The UV–Vis spectra of Complexes 3a–e display a characteristic LLCT (π → π *) band, which was confirmed by TD-DFT calculations. DFT calculations show that the Zn(II) orbitals do not contribute to the HOMO or LUMO, with the latter being primarily found on the two 4-nitrophenyl rings for compounds 3a − e, while the HOMO-1 and HOMO are located on the 4-substituted phenyl rings. Notably, HOMO and LUMO energies and gabs do not differ significantly. Transitions from HOMO to LUMO + 1 are the most important for all ligands. The luminescence properties of solid compounds 3a − e were also investigated at 298 K. Solid state photoluminescence studies reveal that these complexes emit strong yellow-orange luminescence at 450–600 nm with a maximum at about ∼ 500 nm in the cyan region. Furthermore, the thermal stabilities of compounds 3a − e have been investigated.

Treatment of Ti(eta(5)-1-SiMe3C9H6)Cl-3 (1) with LiOR (2a, R = 2,6-tBu2C6H3; 2b, R = 2,6-Ph2C6H3; 2c, R = (C3H7)-C-i; 2d, R= (C4H9)-C-t ) in a 1:1 M ratio produced half-sandwich compounds Ti(eta(5)-1-SiMe3C9H6)Cl-2 (OR) (3a, R = 2,6-(Bu2C6H3)-Bu-t; 3b, R = 2,6-Ph2C6H3; 3c, R = (C3H7)-C-i; 3d, R = (C4H9)-C-t) in high yield. Compounds 3c,d were also accessible, when 1 was reacted with a onefold excess of HOR (2c, R = (C3H7)-C-i; 2d, R = (C4H9)-C-t) in refluxing benzene. The molecular structure of 3b in the solid state was determined by single-crystal X-ray diffraction studies, confirming the piano-stool geometry. Quantum chemical calculations at the B3LYP/6-31g(d)+LANL2DZ level of theory were carried out for 1 and 3a-d in order to better understand and rationalize the nature of bonding and thus demonstrate the effect of different substituents on the structural and electronic properties in these compounds. The studies reveal a high electron density on the Ti(IV) ion for 3c and 3d as compared to 3a and 3b, and also showed the possibility of controlling and fine tuning the electron density on the Ti(IV) ion through the introduction of different alkyloxy or aryloxy substituents. (C) 2018 Elsevier B.V. All rights reserved.

Titanocene dichloride, [Ti]Cl-2 (1) ([Ti] = Ti(eta(5)-C5H4SiMe3)(2)), with one equiv. of the lithium thiolates LiSCHR-2-(C4H3S)-C-c (2a, R = H; 2b, R = Me) gave the appropriate [Ti](Cl)(SCHR-2-(C4H3S)-C-c) compounds (3a, R = H; 3b, R = Me) under mild reaction conditions. Further treatment of 3a,b with another equiv. of thiolates 2a,b produced the respective bis(thiolates) species [Ti](SCHR-2-(C4H3S)-C-c)(2) (4a,b). Titanocenes 4a,b are also accessible, when 1 is reacted with 2a,b in a 1:2 M ratio. The hydrolysis reaction of 4a,b produced the titanoxane cluster 5, consisting of a [Ti'](6)O-9 cage ([Ti'] = Ti(eta(5)-O5H4 SiMe3)) with a silsesquioxane analog structure. The molecular structure of 5 in the solid state is the first example of a trigonal prismatic Ti-6 polyhedron. Upon treatment of 4a,b with MCl2 (M = Pd, Pt), aiming to obtain heterobimetallic coordination complexes, however, either 1 or 3a,b were formed, depending on the reaction conditions. All the compounds have been characterized by elemental analysis, IR, NMR (H-1, C-13{H-1}) spectroscopy and mass-spectrometry. (C) 2018 Elsevier Ltd. All rights reserved.

A blue coloured polycrystalline solid was obtained from reaction of Cu(HCOO) 2 •2H 2 O (20 mmol) with 4-methylpyridine (3 mL) in 20 mL ethanol at room temperature.Its recrystallization in ethanol produced light blue cubic crystals suitable for X-Ray crystallography.Overall yield = 75 %.Anal.Calc.for C 12 H 16 N 2 O 6 Cu (m.w.347.81)C 41.44, H 4.64, N 8.05 %; Found: 41.46, H 4.62, N 8.06 %.On a glass fibre a light blue cubic crystal was mounted and all measurements were performed on BRUKER SMART Synthesis and Crystal Structure of Diaquodiformatodi(4-methyl pyridine)copper(II)

The preparation of the shape-persistent carbosilane-functionalized porphyrins H2TPP(4-SiRR'Me)4, Zn(II)-TPP(4-SiRR'Me)4 (R = R' = Me, CH2CH=CH2, CH2CH2CH2OH; R = Me, R' = CH2CH=CH2, CH2CH2CH2OH; TPP = tetraphenyl porphyrin), H2TPP(4-Si(C6H4-1,4-SiRR'Me)3)4, and Zn(II)-TPP(4-Si(C6H4-1,4-SiRR'Me)3)4 (R = R' = Me, CH2CH=CH2; R = Me, R' = CH2CH[double bond, length as m-dash]CH2) using the Lindsey condensation methodology is described. For a series of five samples their structures in the solid state were determined by single crystal X-ray structure analysis. The appropriate 0th and 1st generation porphyrin-based 1,4-phenylene carbosilanes form 2D and 3D supramolecular network structures, primarily controlled by either π-π interactions (between pyrrole units and neighboring phenylene rings) or directional molecular hydrogen recognition and zinc-oxygen bond formation in the appropriate hydroxyl-functionalized molecules. UV-Vis spectroscopic studies were carried out in order to analyze the effect of the dendritic branches on the optical properties of the porphyrin ring.

The reaction of 1-substituted benzyl-1H-1,2,3-triazole-4-carbohydrazides 2a-h with equimolar amounts of isothiocynate produces 1-(1-substituted benzyl-1H-1,2,3-triazole-4-arbonyl)-N-phenylhydrazinecarbothioamide 3a-h. Treatment of 3a-h with sodium hydroxide afforded 5-(1- substituted benzyl-1H-1,2,3-triazol-4-yl)-4-phenyl-4H-1,2,4-triazole-3-thiol 4a-h. Nucleophlic addition of the corresponding sodium salts of 4a-h to alkyl halide (methyl iodide or benzyl bromide) affords the 1-substituted benzyl-4-(5-(alkylthio)-4-phenyl-4H-1,2,4-triazol-3-yl)-H-1,2,3-triazole 5a-h and 6a-h.

A convenient synthesis method was developed for the preparation of C-stapled homodimeric bis-lexitropsins connected through the nitrogen atoms of the central pyrrole ring with a bis-methylene linker. This lexitropsin is designed as a standard for other bis-lexitropsins with longer chains in biological evaluation and NMR studies. The key step in this method is the treatment of ethyl 4-nitropyrrole-2-carboxylate with flame-dried potassium carbonate in DMF followed by the addition of 1,2-dibromoethane to form the 1,2-dipyrroloethane derivative.

The synthesis and reaction behavior of heterobimetallic {cis-[Pt](μ-σ,π-CCPh)2}[Cu(NCMe)]BF4 (I) is described. On addition of cis-[Pt](CCPh)2 to I trimetallic {[cis-[Pt](μ-σ,π-CCPh)2]2Cu}BF4 is formed in a consecutive reaction sequence. The thereby observed intermediates could be characterized by single X-ray structure determinations.

An entry from the Cambridge Structural Database, the world’s repository for small molecule crystal structures. The entry contains experimental data from a crystal diffraction study. The deposited dataset for this entry is freely available from the CCDC and typically includes 3D coordinates, cell parameters, space group, experimental conditions and quality measures.

2,6-Biphenyl-1,4-diselenafulvene (1) was prepared by air oxidation of PhC= CSe-. Treatment of 1 with equimolar amounts of Fe-2(CO)(9) produced (mu(3)-Se)(2)Fe-3(CO)(9)(2). Compound 1 was characterized by elemental analysis, IR, H-1-, C-13{H-1}-NMR spectroscopy and by X-ray structure determination, while compound 2 was characterized by elemental analysis, IR and EIMS spectrometry.

The electronic interaction between the iron atom and the indenyl ligands with one and two trimethylsilyl substituents in different isomeric positions in bis(indenyl)iron has been studied using cyclic voltammetry and UV–vis spectroscopy. Results and interpretation are supported by theoretical PM3-calculations.

The synthesis of the bis(eta(5)-indenyl)iron sandwich complexes (eta(5)-1-SiMe3-C9H6)(2)Fe (3a), (eta(5)-2-SiMe3-C9H6)(2)Fe (3b), [eta(5)-1,2-(SiMe3)(2)C9H5](2)Fe (4a) and [eta(5)-1,3-(SiMe3)(2)C9H5](2)Fe (4b), by the reaction of the appropriate lithium indenide salts [prepared from 1-SiMe3-C9H7 (2a), 2-SiMe3-C9H7 (2b), 1,2-(SiMe3)(2)C9H6 (2c) or 1,3-(SiMe3)(2)C9H6 (2d)] with ferrous chloride (1) in a 2:1 molar ratio is discussed. The solid-state structure of 4b was determined by single-crystal X-ray diffractometry. Complex 4b exists in a gauche conformation, showing that the indenyl ligands are sterically imposed by the bulk of the Me3Si substituents. The average Fe-C distance is 2.091(3) Angstrom. Cyclovoltammetric studies indicate that 3 and 4 are redox-active with one-electron oxidations [E-1/2 = -270 to -360 mV versus Fc/Fc(+), Fc = (eta(5)-C5H5)(2)Fe]. (C) 2003 Elsevier B.V. All rights reserved.