Ferrocenophanium Stability and Catalysis.

Ferrocenium catalysis is a vibrant research area, and an increasing number of ferrocenium-catalyzed processes have been reported in the recent years. However, the ferrocenium cation is not very stable in solution, which may potentially hamper catalytic applications. In an effort to stabilize ferrocenium-type architectures by inserting a bridge between the cyclopentadienyl rings, we investigated two ferrocenophanium (or -ferrocenium) cations with respect to their stability and catalytic activity in propargylic substitution reactions.

Robustness of hydrogen bonding in the construction of supramolecular architectures in protonated perchlorate salts.

Five new multicomponent salts of perchloric acid with a series of substituted anilines and N-heterocyclic amines namely Diphenylaminium perchlorate (DPAPC) (1), 2, 5-dichloroanilinium perchlorate (25DAP) hydrate (2), 4-Methylanilinium perchlorate (4MAPC) (3), 4-diamino-6-methyl-1, 3, 5-triazin-1-ium hydrogen perchlorate (24DAMTHP) (4), and 8-hydroxyquinolinium hydrogen perchlorate (8HQP) (5) were prepared and structurally characterized. The entire complexes were subjected to FTIR and elemental analysis. A vast family of intermolecular contacts N-H…O, O-H…O, N-H…N, and C-H…O was observed, which are key ingredient in the generation of privileged supramolecular self-assemblies appeared as one-dimensional chain, two-dimensional ladder, and helix.

Ligand Isomerism in Coordination Cages.

Complexation reactions of palladium(II) nitrate with a set of 3-pyridyl appended nonchelating bidentate ligands possessing regioisomeric phenylene-diurea functionalities as spacers were carried out. The ligands utilized in this study are 1,1'-(1,2-phenylene)bis(3-(pyridin-3-yl)urea), L1; 1,1'-(1,3-phenylene)bis(3-(pyridin-3-yl)urea), L2; and 1,1'-(1,4-phenylene)bis(3-(pyridin-3-yl)urea), L3. The complexation reactions of the ligands (L1, L2, and L3) with palladium(II) produced single discrete isomeric cages (1, 2, and 3) of PdL formulation in each case and thereby illustrated ligand-isomerism in coordination cages.

Crystal structure of bis-(2-amino-anilinium) hydrogen phosphate.

The asymmetric unit of the title compound, 2C6H9N2 (+)·HPO4 (2-), comprises two 2-amino-anilinium cations and one hydrogen phosphate dianion. In the crystal, the HPO4 (2-) dianions are linked by O-H⋯O hydrogen bonds into chains along [100]. The inorganic anionic chains and organic cations are linked by N-H⋯O and N-H⋯N hydrogen bonds, forming a two-dimensional supra-molecular network extending parallel to (001).

Hypoelectronic 8-11-Vertex Irida- and Rhodaboranes.

A series of novel isocloso-diiridaboranes [(Cp*Ir)2B6H6], 1, 2; [1,7-(Cp*Ir)2B8H8], 4; [1,4-(Cp*Ir)2B8H8], 5; [(Cp*Ir)2B9H9], 8; isonido-[(Cp*Ir)2B7H7], 3; and 10-vertex cluster [5,7-(Cp*Ir)2B8H12], 6 (Cp* = η(5)-C5Me5) have been isolated and structurally characterized from the pyrolysis of [Cp*IrCl2]2 and BH3·thf. On the other hand, the corresponding rhodium system afforded 10- and 11-vertices clusters [5-(Cp*Rh)B9H13)], 7, and [(Cp*Rh)2B9H9], 9, respectively. Clusters 1 and 2 are topological isomers.

Benzoindolium-triarylborane conjugates: a ratiometric fluorescent chemodosimeter for the detection of cyanide ions in aqueous medium.

Based on benzo[e]indolium and dimesitylborylbenzaldehyde a new ratiometric fluorescent chemodosimeter, C41H43BIN (3) has been synthesized and characterized by (1)H, (13)C NMR spectroscopy, mass spectrometry and single crystal X-ray crystallography. Probe 3 was found to be highly selective and sensitive toward cyanide (CN(-)) ions in aqueous medium even in the presence of other competing anions like F(-), Cl(-), Br(-), I(-), H2PO4(-), HCO3(-) and AcO(-). The detection limit was calculated to be 7.

Gallium and indium complexes containing the bis(imino)phenoxide ligand: synthesis, structural characterization and polymerization studies.

A series of gallium and indium complexes containing a bis(imino)phenolate ligand framework were synthesized and completely characterized with different spectroscopic techniques. The molecular structures of a few complexes were determined using single crystal X-ray diffraction studies. These compounds were found to be extremely active towards the bulk ring opening polymerization (ROP) of lactides yielding polymers with high number average molecular weight (Mn) and controlled molecular weight distributions (MWDs).

A dihydrogen phosphate anionic network as a host lattice for cations in 1-methylpiperazine-1,4-diium bis(dihydrogen phosphate) and 2-(pyridin-2-yl)pyridinium dihydrogen phosphate-orthophosphoric acid (1/1).

In the salt 1-methylpiperazine-1,4-diium bis(dihydrogen phosphate), C5H13N2(2+)·2H2PO4(-), (I), and the solvated salt 2-(pyridin-2-yl)pyridinium dihydrogen phosphate-orthophosphoric acid (1/1), C10H9N2(+)·H2PO4(-)·H3PO4, (II), the formation of O-H...

Octadecanuclear gear wheels by self-assembly of self-assembled "double saddle"-type coordination entities: molecular "rangoli".

A series of self-assembled "double saddle"-type trinuclear complexes of [Pd3L'3L2] formulation have been synthesized by complexation of a series of cis-protected palladium(II) components with a slightly divergent "E-shaped" non-chelating tridentate ligand, 1,1'-(pyridine-3,5-diyl)bis(3-(pyridin-3-yl)urea (L). The cis-protecting agents L' employed in the study are ethylenediamine (en), tetramethylethylenediamine (tmeda), 2,2'-bipyridine (bpy), and 1,10-phenanthroline (phen), for 1, 2, 3, and 4, respectively. The crystal structures of [Pd3(tmeda)3(L)2](NO3)6 (2), [Pd3(bpy)3(L)2](NO3)6 (3), and [Pd3(phen)3(L)2](NO3)6 (4) unequivocally support the new architecture.

N-H∙∙∙O, O-H∙∙∙O hydrogen-bonded supramolecular sheet formation in the bis(2-aminoanilinium) fumarate, 3-methylanilinium hydrogen fumarate and 4-chloroanilinium hydrogen fumarate salts.

In bis(2-aminoanilinum) fumarate, 2C₆H₉N₂⁺·C₄H₂O₄²⁻, (I), the asymmetric unit consists of two aminoanilinium cations and one fumarate dianion, whereas in 3-methylanilinium hydrogen fumarate, C₇H₁₀N⁺·C₄H3O₄⁻, (II), and 4-chloroanilinium hydrogen fumarate, C₆H₇ClN⁺·C₄H3O₄⁻, (III), the asymmetric unit contains two symmetry-independent hydrogen fumate anions and anilinium cations with a slight difference in their geometric parameters; the two salts are isostructural. In (II) and (III), the carboxylic acid H atoms of the anions are disordered across both ends of the anion, with equal site occupancies of 0.50.

Self-assembled supramolecular sheet- and channel-type frameworks in the p-phenetidinium hydrogen phthalate and cyclohexylaminium hydrogen phthalate hemihydrate salts.

The title compounds, p-phenetidinium hydrogen phthalate (or 4-ethoxyanilinium 2-carboxybenzoate), C(8)H(12)NO(+)·C(8)H(5)O(4)(-), (I), and cyclohexylaminium hydrogen phthalate hemihydrate (or cyclohexylaminium 2-carboxybenzoate hemihydrate), C(6)H(14)N(+)·C(8)H(5)O(4)(-)·0.5H(2)O, (II), form two- and one-dimensional supramolecular networks, respectively. In (I), the anionic-cationic network consists of R(3)(2)(6) and R(4)(4)(16) hydrogen-bonded rings forming a two-dimensional sheet along the (001) plane.

Dihydrogen phosphate mediated supramolecular frameworks in 2- and 4-chloroanilinium dihydrogen phosphate salts.

The title compounds, 2-chloroanilinium dihydrogen phosphate (2CADHP) and 4-chloroanilinium dihydrogen phosphate (4CADHP), both C(6)H(7)NCl(+) x H(2)PO(4)(-), form two-dimensional supramolecular organic-inorganic hybrid frameworks. In 2CADHP, the dihydrogen phosphate anions form a double-stranded anionic chain generated parallel to the [010] direction through O-H..

1,3-Dicyclo-hexyl-1-(4-nitro-benzo-yl)urea.

In the title compound, C(20)H(27)N(3)O(4), both cyclo-hexane rings adopt chair conformations. The benzene ring and the amide group are oriented at a dihedral angle of 62.1 (2)°.

N-H...O and O-H...O hydrogen-bonded supramolecular networks in 4-chloroanilinium, 2-hydroxyanilinium and 3-hydroxyanilinium hydrogen phthalates.

The title salts, 4-chloroanilinium hydrogen phthalate (PCAHP), C6H7ClN+.C8H5O4-, 2-hydroxyanilinium hydrogen phthalate (2HAHP), C6H8NO+.C8H5O4-, and 3-hydroxyanilinium hydrogen phthalate (3HAHP), C6H8NO+.

10-[2-(Dimethyl-amino)eth-yl]-9-(4-methoxy-phen-yl)-3,3,6,6-tetra-methyl-3,4,6,7,9,10-hexa-hydro-acridine-1,8(2H,5H)-dione.

In the title compound, C(28)H(38)N(2)O(3), the central ring of the acridinedione system adopts a boat conformation, while one of the outer rings adopts a half-chair conformation and the conformation of the other outer ring is between a sofa and a half-chair. The acridinedione system is buckled, with an angle of 22.01 (3)°.