H2O + Fe(NO3)3 + Ni(NO3)2 ternary system isotherms at 0 °C and 30 °C

H₂O + Ni(NO₃)₂ binary system were investigated in the temperature range from −25 °C to 55 °C. The solid-liquid equilibria of the ternary system H₂O + Fe(NO₃)₃ + Ni(NO₃)₂ were studied using a synthetic method based on conductivity measurements. Tow isotherms were established at 0 °C and 30 °C, and the appearing stable solid phases are iron nitrate nonahydrate (Fe(NO₃)₃·9H₂O), iron nitrate hexahydrate (Fe(NO₃)₃·6H₂O), nickel nitrate hexahydrate (Ni(NO₃)₂·6H₂O) and nickel nitrate tetrahydrate (Ni(NO₃)₂·4H₂O).     

Reactivity of M(en)Cl2 (M = Pd/Pt,en = 1,2-diaminoethane) with N,N′-bis(salicylidene)-p-phenylenediamine: Binding with hexafluorobenzene

Schiff base N,N′-bis(salicylidene)-p-phenylenediamine (LH₂) complexed with Pt(en)Cl₂ and Pd(en)Cl₂ provided [Pt(en)L]₂ · 4PF₆ (1) and Pd(Salen) (2) (Salen = N,N′-bis(salicylidene)-ethylenediamine), respectively, which were characterized by their elemental analysis, spectroscopic data and X-ray data. A solid complex obtained by the reaction of hexafluorobenzene (hfb) with the representative complex 1 has been isolated and characterized as 3 (1 · hfb) using UV–Vis, NMR (¹H, ¹³C and ¹⁹F) data. A solid complex of hfb with a reported Zn-cyclophane 4 has also been prepared and characterized 5 (4 · hfb) for comparison with complex 3. The association of hfb with 1 and 4 has also been monitored using UV–Vis and luminescence data.     

Synthesis,spectroscopic characterization and thermal behavior of cadmium(II) complexes of S-methyldithiocarbazate (SMDTC) and S-benzyldithiocarbazate (SBDTC): X-ray crystal structure of [Cd(SMDTC)3] · 2NO3

Two new cadmium(II) complexes of the empirical formulae [Cd(SMDTC)₃] · 2NO₃ (1) and [Cd(SBDTC)₂] · 2NO₃ (2) have been synthesized and characterized by elemental analyses, UV–Vis, IR, ¹H NMR and TGA techniques. In complex 1, the six coordination sites around cadmium are occupied by three neutral SMDTC molecules with N and S donor atoms from each ligand molecule, whereas in complex 2 the cadmium center is four coordinated with two relatively larger SBDTC ligands chelating with N and S donor atoms in the neutral thione form. In the solid state, thermal gravimetric analysis shows that both complexes are relatively volatile in nature and undergo facile thermal decomposition above 120 °C to form the metal sulfide followed by stepwise loss of ligand molecules. The crystal and molecular structure of complex 1 has been established by the X-ray diffraction method. The central cadmium(II) atom has an octahedral geometry with three five-membered chelate rings formed by SMDTC ligands. The crystal structure consists of parallel layers of cations and anions. The SMDTC molecules in cations are arranged with their N donor groups directed towards the anion layer in an alternating fashion and form hydrogen bonds with the O atoms of the anion.     

A pyrazole-based orthogonal ferromagnetically coupled [2 × 2] homoleptic square Cu4 grid: Magnetostructural correlations

The synthesis and structure of a pyrazole-based orthogonal ferromagnetically coupled tetracopper(II) 2 × 2 homoleptic grid complex [Cu₄(PzOAPyz)₄(ClO₄)₂](ClO₄)₂ · 6H₂O (1), formed by the reaction between the ditopic ligand PzOAPyz and Cu(ClO₄)₂ · 6H₂O, are described. The ligand contains terminal pyrazole and pyrazine residues bound to a central flexible diazine subunit (N–N) as well as one potentially bridging alkoxo group. The two adjacent metal centers are linked by an alkoxo oxygen forming essentially a square Cu₄(μ-O₄) cluster. In the Cu₄(μ-O₄) core, out of the four copper centers, two copper centers are penta-coordinated and the remaining two are hexa-coordinated. In each case of hexa-coordination, the sixth position is occupied by one of the oxygen atoms of a coordinated perchlorate ion. Complex 1 has been characterized structurally and magnetically. Although the large Cu–O–Cu bridge angles (137–138°) and short Cu–Cu distances (3.964–3.970 Å) are suitable for the transmission of the expected antiferromagnetic coupling, the square-based Cu₄(μ-O₄) cluster exhibits an intramolecular ferromagnetic exchange (J = 7.47 cm⁻¹) between the metal centers with an S = 2 magnetic ground state associated with the quasi orthogonal arrangement of the magnetic orbitals (d_x2-y2${\text{d}}_{x^2-y^2}$). The exchange pathway parameters have been evaluated from density functional calculations.     

Dimolybdenum complexes containing anions of N,N′-bis(pyrimidine-2-yl)formamidine and N-(2-pyrimidinyl)formamide

The reactions of Mo₂(O₂CCH₃)₄ with different equivalents of N,N′-bis(pyrimidine-2-yl)formamidine (HL1) and N-(2-pyrimidinyl)formamide (HL2) afforded dimolybdenum complexes of the types Mo₂(O₂CCH₃)(L1)₂(L2) (1) trans-Mo₂(L1)₂(L2)₂ (2) cis-Mo₂(L1)₂(L2)₂ (3) and Mo₂(L2)₄ (4). Their UV–Vis and NMR spectra have been recorded and their structures determined by X-ray crystallography. Complexes 2 and 3 establish the first pair of trans and cis forms of dimolybdenum complexes containing formamidinate ligands. The L1 ligands in 1–3 are bridged to the metal centers through two central amine nitrogen atoms, while the L2 ligands in 1–4 are bridged to the metal centers via one pyrimidyl nitrogen atom and the amine nitrogen atom. The Mo–Mo distances of complexes 1 [2.0951(17) Å], 2 [2.103(1) Å] and 3 [2.1017(3) Å], which contain both Mo?N and Mo?O axial interactions, are slightly longer than those of complex 4 [2.0826(12)–2.0866(10) Å] which has only Mo?O interactions.     

Quantum chemistry studies on the Ru-M interactions and the P NMR in [Ru(CO)3(Ph2Ppy)2(MCl2)] (M = Zn, Cd, Hg)

To study the Ru-M interactions and their effects on ³¹P NMR, complexes [Ru(CO)₃(Ph₂Ppy)₂] (py = pyridine) (1) and [Ru(CO)₃(Ph₂Ppy)₂MCl₂] (M = Zn, 2; Cd, 3; Hg, 4) were calculated by density functional theory (DFT) PBE0 method. Moreover, the PBE0-GIAO method was employed to calculate the ³¹P chemical shifts in complexes. The calculated ³¹P chemical shifts in 1-3 follow 2 > 3 > 1 which are consistent to experimental results, proving that PBE0-GIAO method adopted in this study is reasonable. This method is employed to predict the ³¹P chemical shift in designed complex 4. Compared with 1, the ³¹P chemical shifts in 2-4 vary resulting from adjacent Ru-M interactions. The Ru → M or Ru ← M charge-transfer interactions in 2-4 are revealed by second-order perturbation theory. The strength order of Ru → M interactions is the same as that of the P-Ru → M delocalization with Zn > Cd > Hg, which coincides with the order of ³¹P NMR chemical shifts. The interaction of Ru → M, corresponding to the delocalization from 4d orbital of Ru to s valence orbital of M²⁺, results in the delocalization of P-Ru → M, which decreases the electron density of P nucleus and causes the downfield ³¹P chemical shifts. Except 2, the back-donation effect of Ru ← M, arising from the delocalization from s valence orbital of M²⁺ to the valence orbital of Ru, is against the P-Ru → M delocalization and results in the upfield ³¹P chemical shifts in 4. Meanwhile, the binding energies indicate that complex 4 is stable and can be synthesized experimentally. However, as complex [Ru(CO)₃(Ph₂Ppy)₂HgCl]⁺5 is more stable than 4, the reaction of 1 with HgCl₂ only gave 5 experimentally.     

Study of oxygen adsorption on β-Si3N4(0 0 0 1) by the density functional theory

The density functional theory (DFT) B3LYP method is used to theoretically investigate the interaction of O₂ with the β-Si₃N₄ surface (0 0 0 1) at 1200 °C. All the calculations have been performed at the 6-31G^∗ basis set level using H-saturated cluster. From the total energy minimization, the chemisorption on the center of the molecule lying above an Si site and the molecular axis paralleling to the surface is the most stable. After adsorption, the O–O bond is easier to dissociate compared to the free O₂. The electron transferred from the substrate to the O₂ molecule occupies the O₂ anti-bonding orbital, thus leading to a weakening off the bond strength, which is reflected by the elongated O₂ bond length. The changing trend of the O–O population and vibrational frequency is consistent with the change of the O–O bond length. The significant chemisorption energy and the short adsorption bond length indicate that the oxidation occurs on the β-Si₃N₄(0 0 0 1) surface at 1200 °C more easily.     

Synthesis, characterization and Schlenk equilibrium studies of methylmagnesium compounds with O- and N-donor ligands - the unexpected behavior of [MgMeBr(pmdta)] (pmdta = N,N,N′,N″,N″-pentamethyldiethylenetriamine)

MgMe₂ (1) was found to react with 1,4-diazabicyclo[2.2.2]octane (dabco) in tetrahydrofuran (thf) yielding a binuclear complex [{MgMe₂(thf)}₂(μ-dabco)] (2). Furthermore, from reactions of MgMeBr with diglyme (diethylene glycol dimethyl ether), NEt₃, and tmeda (N,N,N′,N′-tetramethylethylenediamine) in etheral solvents compounds MgMeBr(L), (L = diglyme (5); NEt₃ (6); tmeda (7)) were obtained as highly air- and moisture-sensitive white powders. From a thf solution of 7 crystals of [MgMeBr(thf)(tmeda)] (8) were obtained. Reactions of MgMeBr with pmdta (N,N,N′,N″,N″-pentamethyldiethylenetriamine) in thf resulted in formation of [MgMeBr(pmdta)] (9) in nearly quantitative yield. On the other hand, the same reaction in diethyl ether gave MgMeBr(pmdta) · MgBr₂(pmdta) (10) and [{MgMe₂(pmdta)}₇{MgMeBr(pmdta)}] (11) in 24% and 2% yield, respectively, as well as [MgMe₂(pmdta)] (12) as colorless needle-like crystals in about 26% yield. The synthesized methylmagnesium compounds were characterized by microanalysis and ¹H and ¹³C NMR spectroscopy. The coordination-induced shifts of the ¹H and ¹³C nuclei of the ligands are small; the largest ones were found in the tmeda and pmdta complexes. Single-crystal X-ray diffraction analyses revealed in 2 a tetrahedral environment of the Mg atoms with a bridging dabco ligand and in 8 a trigonal-bipyramidal coordination of the Mg atom. The single-crystal X-ray diffraction analyses of [MgMe₂(pmdta)] (12) and [MgBr₂(pmdta)] (13) showed them to be monomeric with five-coordinate Mg atoms. The square-pyramidal coordination polyhedra are built up of three N and two C atoms in 12 and three N and two Br atoms in 13. The apical positions are occupied by methyl and bromo ligands, respectively. Temperature-dependent ¹H NMR spectroscopic measurements (from 27 to −80 °C) of methylmagnesium bromide complexes MgMeBr(L) (L = thf (4); diglyme (5); NEt₃ (6); tmeda (7)) in thf-d₈ solutions indicated that the deeper the temperature the more the Schlenk equilibria are shifted to the dimethylmagnesium/dibromomagnesium species. Furthermore, at −80 °C the dimethylmagnesium compounds are predominant in the solutions of Grignard compounds 4-6 whereas in the case of the tmeda complex7 the equilibrium constant was roughly estimated to be 0.25. In contrast, [MgMeBr(pmdta)] (9) in thf-d₈ revealed no dismutation into [MgMe₂(pmdta)] (12) and [MgBr₂(pmdta)] (13) even up to −100 °C. In accordance with this unexpected behavior, 1:1 mixtures of 12 and 13 were found to react in thf at room temperature yielding quantitatively the corresponding Grignard compound 9. Moreover, the structures of [MgMeBr(pmdta)] (9c), [MgMe₂(pmdta)] (12c), and [MgBr₂(pmdta)] (13c) were calculated on the DFT level of theory. The calculated structures 12c and 13c are in a good agreement with the experimentally observed structures 12 and 13. The equilibrium constant of the Schlenk equilibrium (2 9c ? 12c + 13c) was calculated to be K_gas = 2.0 × 10⁻³ (298 K) in the gas phase. Considering the solvent effects of both thf and diethyl ether using a polarized continuum model (PCM) the corresponding equilibrium constants were calculated to be K_thf = 1.2 × 10⁻³ and K_ether = 3.2 × 10⁻³ (298 K), respectively.     

Conformational study of lanthanide(III) complexes of N-(2-salicylaldiminatobenzyl)-1-aza-18-crown-6 by using X-ray and ab initio methods

A structural study of lanthanide complexes with the deprotonated form of the monobracchial lariat ether N-2-salicylaldiminatobenzyl-aza-18-crown-6 (L⁴) (Ln = La(III)–Tb(III)) is presented. Attempts to isolate complexes of the heaviest members of the lanthanide series were unsuccessful. The X-ray crystal structures of [Pr(L⁴)(H₂O)](ClO₄)₂ · H₂O · C₃H₈O and [Sm(L⁴)(H₂O)](ClO₄)₂ · C₃H₈O show the metal ion being bound to the eight donor atoms of the ligand backbone. Coordination number nine is completed by the oxygen atom of an inner-sphere water molecule. Two different conformations of the crown moiety (labelled as A and B) are observed in the solid state structure of the Pr(III) complex, while for the Sm(III) complex only conformation A is observed. The complexes were also characterized by means of theoretical calculations performed in vacuo at the HF level, by using the 3-21G^∗ basis set for the ligand atoms and a 46 + 4fⁿ effective core potential for lanthanides. The optimized geometries of the Pr(III) and Sm(III) complexes show an excellent agreement with the experimental structures obtained from X-ray diffraction studies. The calculated relative energies of the A and B conformations for the different [Ln(L⁴)(H₂O)]²⁺ complexes (Ln = La, Pr, Sm, Ho or Lu) indicate a progressive stabilization of the A conformation with respect to the B one upon decreasing the ionic radius of the Ln(III) ion. For the [Ln(L⁴)(H₂O)]²⁺ systems, most of the calculated bond distances between the metal ion and the coordinated donor atoms decrease along the lanthanide series, as usually observed for Ln(III) complexes. However, our ab initio calculations provide geometries in which the Ln–O(5) bond distance [O(5) is an oxygen atom of the crown moiety] increases across the lanthanide series from Sm(III) to Lu(III).     

Syntheses, crystal structures and luminescent properties of two novel lanthanide/4-pya complexes: [Ln(4-pya)3(H2O)2]2 (Ln = Eu, La; 4-pya = trans-4-pyridylacrylate)

Reactions of Ln₂O₃ and trans-4-pyridylacrylic acid (4-Hpya) in EtOH/H₂O or MeOH/H₂O produced two new lanthanide/4-pya complexes [Ln(4-pya)₃(H₂O)₂]₂ (1: Ln = Eu; 2: Ln = La) in low yields. However, reactions of LnCl₃ · 6H₂O with 4-Hpya/aqueous ammonia in EtOH/H₂O or MeOH/H₂O gave rise to 1 or 2 in higher yields. Both compounds were structurally characterized by elemental analysis, IR spectroscopy and X-ray analysis. Compounds 1 · 2EtOH · 2H₂O and 2 · 2MeOH · 2H₂O were confirmed to possess one-dimensional polymeric chain structures. In the structure of 1, each Eu(III) adopts a monocapped square-antiprism coordination geometry and each dimer [Eu(4-pya)₃(H₂O)₂]₂ within the chain is interconnected by two pairs of different bridging 4-pya ligands. On the other hand, each La(III) of 2 takes a bicapped square-antiprism coordination geometry and each dimer [La(4-pya)₃(H₂O)₂]₂ within the chain is linked by two pairs of tridentate bridging 4-pya ligands. The luminescent properties of 1 and 2 in the solid state were investigated.     

The DFT and ab initio investigations on the mechanism of CF3O2 + H reaction

The mechanisms for the reaction of CF₃O₂ with atomic hydrogen were studied with ab initio and DFT methods. The results reveal that the reaction could take place on the singlet and triplet potential energy surfaces (PES). For the singlet PES, addition/elimination and substitution mechanisms are determined, and the former one is dominant. The most favorable channel involves the association of CF₃O₂ with H atom to form CF₃O₂H (IM1) via a barrierless process, and then the O–O bond dissociates to give out CF₃O + OH. The secondary product might be CF₃OH + O, formed from the O–O bond cleavage in the initial adduct CF₃O(H)O (IM2). Other products such as CF₃ + O₂H, HF + CF₂O₂ and O₂ + CHF₃ are of no importances because of higher barriers. On the triplet PES, only substitution mechanism is located. With higher barriers involving, the channels on the triplet PES could be negligible compared with the channels on the singlet PES.     

Two-stage formation of chloro (N-o-chlorobenzamido-meso-tetraphenylporphyrinato) zinc(II) methylene chloride solvate: Zn(N-NHCO(o-Cl)C6H4-tpp)Cl · CH2Cl2

The coordinating properties of N-o-chlorobenzamido-meso-tetraphenylporphyrin (N-NHCO(o-Cl)C₆H₄-Htpp; 11) have been investigated for the Zn²⁺ ion. Insertion of Zn results in the formation of the zinc complex Zn(N-NCO(o-Cl)C₆H₄-tpp)(MeOH) · MeOH (12 · MeOH). The diamagnetic 12 · MeOH can be transformed into the diamagnetic Zn(N-NHCO(o-Cl)C₆H₄-tpp)Cl · CH₂Cl₂ (13 · CH₂Cl₂) in a reaction with aqueous hydrogen chloride (2%). X-ray structures for 12 · MeOH and 13 · CH₂Cl₂ have been determined. The coordination sphere around the Zn²⁺ ion in 12 · MeOH is a distorted trigonal bipyramid with N(2), N(4) and O(2) lying in the equatorial plane, whereas for the Zn²⁺ ion in 13 · CH₂Cl₂, it is a square-based pyramid in which the apical site is occupied by the Cl(1) atom.     

Synthesis and characterization of coordination polymers of a carboxylato cyclophane with metal [Zn(II) and Cd(II)]-2,2′-bipyridines

N,N′,N′′,N′′′-Tetrakis(3-carboxy-propionyl)-1,6,20,25-tetraaza-[6.1.6.1] paracyclophane, H₄cp has been complexed with metal (Zn(II) and Cd(II)) 2,2′-bipyridyls. The resulting complexes of the composition [{Zn(2,2′-bpy)}₂(cp)]_n·4H₂O 1 and [{Cd(2,2′-bpy)}₂(cp)]_n·5H₂O 2 (2,2′-bpy = 2,2′-bipyridine) have been characterized using spectroscopic (IR, solid state UV–Vis), elemental analysis and single-crystal X-ray diffraction measurements. In these complexes the cyclophane coordinates in different modes, and in complex 2, Cd(II) is hepta-coordinated. However, under harsh reaction conditions (using excess nitric acid and a longer reaction time) debranching of the cyclophane is observed in the reaction of Zn(2,2′-bpy)(NO₃)₂ with H₄cp, and a complex of the composition [Zn(2,2′-bpy)(Suc)]_n3 (suc = succinate) is isolated. Using non-covalent interactions, complexes 1 and 2 provide 3D supramolecular structures, whereas an infinite 1D chain structure is observed for complex 3. The thermal and photoluminescence properties of the complexes have also been studied.     

Piperazinediium,Zr(IV) and Ce(IV) pyridine-2,6-dicarboxylates: Syntheses,characterizations, crystal structures, ab initio HF,DFT calculations and solution studies

The novel title compounds, (pipzH₂)_1.5(pydcH)₃·3.7H₂O, 1, (pipzH₂)[Zr(pydc)₃]·8H₂O, 2 and (pipzH₂)[Ce(pydc)₃]·8H₂O, 3 in which pydcH₂ is pyridine-2,6-dicarboxylic acid and pipz is piperazine were obtained in aqueous solution. The compounds were characterized by IR, ¹H NMR and ¹³C NMR spectroscopy, elemental analyses, and X-ray crystallography. Compound 1 is resulted from proton transfer between pydcH₂ and pipz. However, compounds 2 and 3 are resulted from complexation of 1 and corresponding metallic salts. Both compounds 2 and 3 contain three pyridine-2,6-dicarboxylate species as tridentate ligands, one piperazinediium as counter ion, and eight-uncoordinated water molecules in the asymmetric unit. In both structures each M(IV) is coordinated in a distorted tricapped trigonal prism geometry by three nitrogen and six oxygen atoms of carboxylate groups of three (pydc)²⁻ fragments. In the crystal structures of 1, 2 and 3, extensive O–H···O, N–H···O and C–H···O hydrogen bonds as well as electrostatic forces, C–H···π, C–O···π and π–π stacking play important roles in stabilizing structures. The geometrical parameters of the [M(pydc)₃]²⁻ anionic complexes, where M = Ce(IV), Zr(IV) have been optimized with the B3LYP method of density functional theory (DFT) and ab initio Hartree–Fock (HF) methods for comparison. In addition, we have studied the structures of (pydc)²⁻ anion and its mono and doubly protonated forms, (pydcH)⁻ and pydcH₂. The electronic properties of the anionic complexes and ligands have been investigated based on the natural bond orbital (NBO) analysis at the B3LYP method which verifies that the synergistic effect has been occurred in the title complexes. In solution study of 2, the stoichiometry and stability constant of complexation of pipz, pydc, pydc–pipz proton transfer system and Zr(IV) ion in aqueous solution were investigated by potentiometric method.     

Polymorphism in [Co(SCN)4(ppz-H)2] (ppz,piperazine)

A one-pot reaction of [Co(NO₃)₂ · 6H₂O and piperazine] with NH₄SCN/NaSCN in water–methanol (1:1) solvent leads to two polymorphs of [Co(SCN)₄(ppz-H)₂] (ppz, piperazine) (I and II). X-ray crystal structure reveals both have same space group but the differences in the alignment of pendant SCN⁻ leads to two polymorphs. In I, trifurcated N–H?S hydrogen bonding plays a prominent role in crystal packing leading to S?S interactions between SCN fragments but in II, no such trifurcation arises and thereby the crystal packing occurs through hydrogen bonding interactions only leading to a distinctly different network topology. TG/DSC and FT-IR study reveal they are enantiotropically related.     

A many-body theory of the Ti M2,3-VV Auger-photoelectron coincidence spectroscopy (APECS) spectrum of TiO2(1 1 0)

We calculated the Ti M_2,3-VV Auger-photoelectron coincidence spectroscopy spectrum of TiO₂(1 1 0) by a many-body theory. The spectral main line is governed by the DOS of the two O 2p holes living longer than the Ti ∣cd²L²〉 → ∣L²〉 super Coster-Kronig (sCK) decay. The two O 2p holes are created by the charge transfer core-hole screening at the Ti atomic site. Here c and L are the Ti 3p hole and the ligand O 2p hole, respectively. Analysis of the spectrum shows that the two (or three) CT O 2p holes in the π bonding states are localized, whereas those in the σ bonding states are delocalized. The three localized CT O 2p (π) holes in ∣cd³L³〉 in Ti M_2,3 main line (or satellite) of TiO₂(1 1 0) live longer than the Ti ∣cd³L³〉 → ∣d¹L³〉 sCK decay so that the Coulomb repulsion from the surrounding Ti ions gives the O⁺ ion desorption from the surface.     

Hypervalent triphenyl and diphenyl tin coordination compounds derived from 2-(1H-benzimidazol-2-yl)phenol

Reactions of 2-(1H-benzimidazol-2-yl)phenol (1) and SnPh₃Cl, SnPh₂Cl₂ and SnCl₄ were investigated. One tetracoordinated triphenyltin(IV) compound: triphenyltin-2-(1H-benzimidazol-2-yl)phenolate] (3) and its adducts: [O → Sn] dimethylsulfoxide triphenyltin-[2-(1H-benzimidazol-2-yl)phenolate] (4), [O → Sn] aqua triphenyltin-[2-(1H-benzimidazol-2-yl)phenolate] (5) [O → Sn] ethanol triphenyltin-[2-(1H-benzimidazol-2-yl)phenolate] (6), [N → Sn] pyridine triphenyltin-[2-(1H-benzimidazol-2-yl)phenolate] (7), where 1 acts as a monodentate ligand bound through the phenol oxygen, were obtained. In the pentacoordinated compounds 4-7, the tin atom has tbp geometry. The three phenyl groups are in equatorial positions, whereas the benzimidazole and the Lewis base are in apical positions. Two hexacoordinated tin compounds: diphenyltin-bis[2-(1H-benzimidazol-2-yl-κN)phenolate-κO] (8), dichlorotin-bis[2-(1H-benzimidazol-2-yl-κN)phenolate-κO] (9) bearing two bidentate ligands are reported. The coplanar ligands in 8 and 9 form six membered rings by oxygen and nitrogen coordination. The tin geometry is all-trans octahedral. In 8 the two phenyl groups, and in 9 the two chlorine atoms are perpendicular to the plane of the ligands. Compounds were identified in solution mainly by ¹H, ¹³C and ¹¹⁹Sn NMR and in the solid state by X-ray diffraction analysis.     

Synthesis, structure and dynamic stereochemistry of (O → Si)-chelate N-(trifluorosilylmethyl)-[N-(S)-(1-phenylethyl)]acetamide and 1-(trifluorosilylmethyl)-2-oxoperhydroazepine: Retention of the O → Si coordination in the adduct with KF and 18-crown-6

The novel compounds, N-(trifluorosilylmethyl)-[N-(S)-(1-phenylethyl)]-acetamide (1a) and 1-(trifluorosilylmethyl)-2-oxoperhydroazepine (1b) have been prepared from the corresponding NH-compounds using ClCH₂SiCl₃/Et₃N or ClCH₂SiCl₃/(Me₃Si)₂NH followed by methanolysis or hydrolysis of the reaction mixture in the presence of Lewis bases, and then BF₃ etherate. Potassium-(18-crown-6)-(2-oxoperhydroazepinomethyl)tetrafluorosilicate (2) was synthesized by reaction of the trifluoride (1b) with KF in the presence of 18-crown-6. Using ¹⁹F, ²⁹Si NMR and X-ray diffraction techniques it was established that the silicon atom is pentacoordinate in the trifluorides (1a, b) and hexacoordinate in the adduct 2. Thus the internal coordination of the O → Si bond present in the trifluoride (1b) is retained in the adduct 2.The stereochemical non-rigidity of the trifluorides (1a, b) and the N-(trifluorosilylmethyl)-N-methylacetamide (1c) was investigated using dynamic ¹⁹F NMR spectroscopy. The activation barriers for permutational isomerization are in the range 9.5-10 kcal mol⁻¹. Lower values of ΔG^# for permutation of trifluorides (1a-c) compared to the monofluorides with the coordination core OSiC₃F together with small negative values for the activation entropy implies a non-dissociative mechanism. Quantum-chemical analysis suggests a mechanism involving a turnstile rotation.     

Effect of size of metal ion on MS4N2 chromophore: Synthesis,spectral and single crystal X-ray structural studies on (2,2′-bipyridine)bis(N-cyclohexyl-N-methyldithiocarbamato)M(II) (M = zinc,cadmium)

Isomorphous complexes [Zn(S₂CN(Me)Cy)₂(bipy)] (1) and [Cd(S₂CN(Me)Cy)₂(bipy)] (2) (where Cy(Me)NCS₂⁻ = N-cyclohexyl-N-methyldithiocarbamate anion and bipy = 2,2′-bipyridine) have been synthesised. Their structures and spectroscopic properties have been studied by IR, ¹H and ¹³C NMR spectroscopy and single crystal X-ray analysis. IR spectrum of the complexes show the contribution of thioureide form to the structures. ¹H NMR spectra of the complexes showed the desheilding of methyl protons and H-1 of cyclohexyl group on complexation. The downfield shift of N¹³CS₂, methyl carbon and C-1 of cyclohexyl group carbon signals for 2 (205.5, 36.7 and 64.4 ppm) from the chemical shift value of 1 (204.2, 35.6 and 63.1 ppm) is attributed to the movement of more electron density from dithiocarbamate towards cadmium. Single crystal X-ray structures of 1 and 2 indicate that the central metal atom is in a distorted octahedral environment for both complexes. The presence of added 2,2′-bipyridine ligand in the coordination sphere of M(S₂CN(Me)Cy)₂ increases Zn–S distances and decreases S–Zn–S angles in 1 and slightly increases Cd–S distances in 2. S–Cd–S angles are not affected. This is due to the relatively larger size of the cadmium ion compared to zinc ion which alleviates the strain involved in transformation from tetrahedral to octahedral.