Synthesis and characterization of a new cyclic phosph(V)azane ligand [(C6H5N)P(O)H]2 and its zinc(II) complex

The new cyclic phosph(V)azane ligand [(C₆H₅N)P(O)H]₂ (2) is obtained from the reaction between PCl₃ and PhNH₂ in toluene followed by controlled hydrolysis of the product in an H₂O–CHCl₃ solution. Compound 2 is the first example of P(V) dimer [(µ-NC₆H₅)P(H)=O]₂, a P₂N₂ ring with two P(O)H moieties. The reaction of 2 with ZnCl₂ in a molar ratio of 1?:?1 in tetrahydrofuran yields the cyclophosph(V)azane complex Cl₂Zn[(C₆H₅N)P(O)H]₂ (3) in which Zn–O bonds form directly between a cyclic phosph(V)azane ligand and Zn(II). The products have been characterized by infrared, multinuclear (¹H, ³¹P, ¹³C) NMR, mass spectrometry, and elemental analysis.     

Selenium(IV) fluoride and oxofluoride anions

The [((C₆H₅)₃P)₂N]⁺, [(C₆H₅)₄P]⁺ and [N(CH₃)₄]⁺ salts of SeF₅⁻, SeF₆²⁻ and SeOF₃⁻ and CsSeO₂F were prepared and characterized. Crystal structures were obtained for [((C₆H₅)₃P)₂N][SeF₅] and [((C₆H₅)₃P)₂N][SeOF₃] CH₂Cl₂. In contrast to oxygen-bridged dimeric TeOF₃⁻, the SeOF₃⁻ anion in [((C₆H₅)₃P)₂N][SeOF₃] CH₂Cl₂ is monomeric and represents the first experimentally well determined molecular structure of a monomeric trifluoro-chalcogenite anion. Similarly, [((C₆H₅)₃P)₂N][SeF₅] represents the first example of a structure containing a well-isolated undistorted SeF₅⁻ anion. The NMR and the vibrational spectra and their assignments were re-examined and corrected by comparison with high-level theoretical calculations. Whereas the previously published normal coordinate analysis of SeF₅⁻ is correct, that for SeOF₃⁻ needs major revision.     

Cl/Cl isotope effects in Rh NMR of [RhCln(H2O)6−n] complex anions in hydrochloric acid solution as a unique ‘NMR finger-print’ for unambiguous speciation

A detailed analysis of the ³⁵Cl/³⁷Cl isotope effects observed in the 19.11 MHz ¹⁰³Rh NMR resonances of [RhCl_n(H₂O)_6−n]³⁻ⁿ complexes (n = 3–6) in acidic solution at 292.1 K, shows that the ‘fine structure’ of each ¹⁰³Rh resonance can be understood in terms of the unique isotopologue and in certain instances the isotopomer distribution in each complex. These ³⁵Cl/³⁷Cl isotope effects in the ¹⁰³Rh NMR resonance of the [Rh^35/37Cl₆]³⁻ species manifest only as a result of the statistically expected ³⁵Cl/³⁷Cl isotopologues, whereas for the aquated species such as for example [Rh^35/37Cl₅(H₂O)]²⁻, cis-[Rh^35/37Cl₄(H₂O)₂]⁻ as well as the mer-[Rh^35/37Cl₃(H₂O)₃] complexes, additional fine-structure due to the various possible isotopomers within each class of isotopologues, is visible. Of interest is the possibility of the direct identification of stereoisomers cis-[RhCl₄(H₂O)₂]⁻, trans-[RhCl₄(H₂O)₂]⁻, fac-[RhCl₃(H₂O)₃] and mer-[RhCl₃(H₂O)₃] based on the ¹⁰³Rh NMR line shape, other than on the basis of their very similar δ(¹⁰³Rh) chemical shift. The ¹⁰³Rh NMR resonance structure thus serves as a novel and unique ‘NMR-fingerprint’ leading to the unambiguous assignment of [RhCl_n(H₂O)_6−n]³⁻ⁿ complexes (n = 3–6), without reliance on accurate δ(¹⁰³Rh) chemical shifts.     

N,N-polymethylene-bisadenine complexes with d metal ions

The reaction of N⁹,N^9′-(tri or tetramethylene)-bisadenines (Ade₂C_x; x = 3 or 4) in HCl 2 M at 50 °C with MCl₂ · 2H₂O [M = Zn(II), Cd(II)] yields outer sphere compounds like the previously described [(H-Ade)₂C₃][ZnCl₄] · H₂O (3) and [(H-Ade)₂C₃]₂[Cd₂Cl₈(H₂O)₂] · 4H₂O (4) for Ade₂C₃ and the new {[(H-Ade)₂C₄][Cd₂Cl₆(H₂O)₂] · 2H₂O}_n (5) for Ade₂C₄. On the other hand, only in case of Zn(II) complexes by changing [HCl] to 0.1 M, the inner sphere compounds [H-(Ade)₂C₃(ZnCl₃)] (6) and [H-(Ade)₂C₄(ZnCl₃)] · 1.5H₂O (7) are obtained. X-ray diffraction study of compound 6, which represents the first inner sphere complex with a N⁹,N^9′-bisadenine, shows a zwitterionic form with one adenine ring protonated at N(1) while the other ring is coordinated via N(7) to a ZnCl₃ moiety as in other alkyl-adenine derivatives. In addition, with Ade₂C₄, is also possible to obtain another inner sphere complex: [(H-Ade)₂C₄(ZnCl₃)₂] · 3H₂O (8).     

Reactions of the metallocene dichlorides [M(Cp)2Cl2] (M = Zr, Hf) and [Ti(MeCp)2Cl2] with the pyridine-2,6-dicarboxylate(−2) ligand: Synthesis, spectroscopic characterization and X-ray structures of the products

The reactivity pattern of the 16-electron species [M(Cp)₂Cl₂] (M = Zr, Hf; Cp⁻ = η⁵-C₅H₅⁻) and [Ti(MeCp)₂Cl₂] (MeCp⁻ = η⁵-C₅H₄CH₃⁻) towards the dipicolinate(−2) (dipic²⁻) ligand under mild (ambient temperature) and convenient (aerobic reactions, aqueous media) conditions have been investigated. The syntheses, molecular structures and spectroscopic (IR, ¹H NMR) characterization are reported for the 18-electron products [Zr(Cp)₂(dipic)] (1), [Hf(Cp)₂(dipic)] (2) and [Ti(MeCp)₂(dipic)] (3). The dipic²⁻ ion behaves as N,O,O′-chelating ligand in the three complexes, while the centroids of the Cp⁻ (1, 2) and MeCp⁻ (3) rings formally occupy the fourth and fifth coordination sites about the central metal. The two identical/very similar bite angles of only ∼70° make the dipic²⁻ ligand particularly suited to form stable metallocene derivatives with 5-coordinate geometry. IR and ¹H NMR data are discussed in terms of the known structures and the tridentate chelating mode of the dipic²⁻ ligand.     

Dephosphorylation of paraoxon by hydroxamate ions in micellar media

The rate-surfactant concentration profiles for the reaction of the insecticide paraoxon with hydroxamate ions (R(CO)·NHO⁻, R = CH₃, R = C₆H₅, R = 2-HOC₆H₄) in aqueous solutions of cetyltrimethylammonium salts, CTAX (X⁻ = Br⁻, Cl⁻, SO₃H⁻) have been measured at pH 11.0 at 30 °C. All these profiles are typical of micelle-assisted bimolecular reactions involving interfacial ion exchanges. The salicylhydroxymic acid-CTACl combination is most reactive.     

The synthesis, structure and ethene polymerization activity of octahedral heteroligated (salicylaldiminato)(β-enaminoketonato)titanium complexes: The X-ray crystal structure of {3-Bu-2-(O)C6H3CHN(Ph)}{(Ph)NC(Me)C(H)C(Me)O}TiCl2

Treatment of the mono(salicylaldiminato)titanium complexes {3-Bu^t-2-(O)C₆H₃CHN(Ar)}TiCl₃(THF) (Ar = C₆H₅, 2,4,6-Me₃C₆H₂ or C₆F₅) with the potassium β-enaminoketonates (C₆H₅)NC(CH₃)C(H)C(R)OK (R = CH₃, CF₃) yielded the first examples of heteroligated (salicylaldiminato) (β-enaminoketonato)titanium dichloride complexes. The complex {3-Bu^t-2-(O)C₆H₃CHN(C₆H₅)}{(C₆H₅)NC(CH₃)C(H)C(CH₃)O}TiCl₂ was structurally characterized by X-ray diffraction and has an orientation with trans-O,O,cis-Cl,Cl, cis-N,N distorted octahedral geometry. These complexes polymerize ethene when activated with MAO; the highest productivity, 5650 kg PE (mol metal)⁻¹ h⁻¹ atm⁻¹, was afforded by {3-Bu^t-2-(O)C₆H₃CHN(C₆F₅)}{(C₆H₅)NC(CH₃)C(H)C(CF₃)O}TiCl₂ at 60 °C.     

Synthesis and X-ray structural characterisation of the tetramethylene oxonium derivative of the hydrodecaborate anion. A versatile route for derivative chemistry of [B10H10]

The oxonium derivative P(C₆H₅)₄[2-B₁₀H₉O(CH₂)₄] (1) has been prepared from [B₁₀H₁₀]²⁻ by a solvent-addition reaction route, promoted by Et₂O · BF₃. Its structure has been confirmed by single crystal X-ray analysis. 1 is assumed to be a useful synthon for the derivative chemistry of [B₁₀H₁₀]²⁻. As an illustration, ring-opening reaction occurred in presence of the strong nucleophilic agent OH⁻, giving the monoanionic derivative [P(C₆H₅)₄]₂[2-B₁₀H₉O(CH₂)₄OH] (2).     

Phase transitions and molecular motions in [Cd(H2O)6](BF4)2 studied by DSC, H and F NMR and FT-MIR

Two solid phase transitions of [Cd(H₂O)₆](BF₄)₂ occurring on heating at T_C2=183.3 K and T_C1=325.3 K, with 2 K and 5 K hysteresis, respectively, were detected by differential scanning calorimetry (DSC). High value of entropy changes indicated large orientational disorder of the high temperature and intermediate phase. Nuclear magnetic resonance (¹H NMR and ¹⁹F NMR) relaxation measurements revealed that the phase transitions at T_C1 and T_C2 were associated with a drastic and small change, respectively, of the both spin-lattice relaxation times: T₁(¹H) and T₁(¹⁹F). These relaxation processes were connected with the “tumbling” motions of the [Cd(H₂O)₆]²⁺, reorientational motions of the H₂O ligands, and with the iso- and anisotropic reorientation of the BF₄⁻ anions. The cross-relaxation effect was observed in phase III. The line width and the second moment of the ¹H and ¹⁹F NMR line measurements revealed that the H₂O reorientate in all three phases of the title compound. On heating the onset of the reorientation of 3 H₂O in the [Cd(H₂O)₆]⁺², around the three-fold symmetry axis of these octahedron, causes the isotropic reorientation of the whole cation. The BF₄⁻ reorientate isotropically in the phases I and II, but in the phase III they perform slow reorientation only about three- or two-fold axes. A small distortion in the structure of BF₄⁻ as well as of [Cd(H₂O)₆]²⁺ is postulated. The temperature dependence of the bandwidth of the O-H stretching mode measured by Fourier transform middle infrared spectroscopy (FT-MIR) indicated that the activation energy for the reorientation of the H₂O did not change much at the T_C2 phase transition.     

Melamine-mediated self-assembly of a Cu(II)–methylmalonate complex assisted by π+–π+ and anti-electrostatic H-bonding interactions

A Cu(II)-methylmalonate complex, (C₃H₇N₆)₄[Cu(II)(C₄H₄O₄)₂](H₂O)₄Cl₂ (1) (where C₃H₇N₆ = protonated melamine, C₄H₄O₄ = methylmalonic acid), has been synthesized from aqueous media and its crystal structure was determined by single-crystal X-ray diffraction. The anionic Cu(II)-methylmalonate complex mediated formation of interesting supramolecular assemblies in the solid state by means of ionic interactions with protonated melamine. Moreover, other forces such as antielectrostatic H-bonding and π⁺–π⁺ interactions also play a crucial role in defining the final 3-D architecture of 1. An interesting stacking among protonated melamine molecules is studied by DFT calculations. Lattice water molecules and chlorides form various hydrogen bonds to take part in the self-assembly processes.     

C-S bond formation catalyzed by N-heterocylic carbene palladium phosphine complexes

N-Heterocyclic carbenes (NHCs) are known to be useful ligands for palladium-complex catalysis. It was found that [(NHC)Pd(PPh₃)Cl₂] is an effective pre-catalyst in Pd-catalyzed C-S cross coupling reactions to produce the functionalized sulfides in excellent yields. The turn over frequency (TOF) for the coupling of p-CH₃C₆H₄Br with p-CH₃C₆H₄SH reaches to 6.25 (mol of product) (mole of catalyst)⁻¹ h⁻¹.     

Synthesis and characterization of new paramagnetic tetraaryl derivatives of chromium and molybdenum

The low-temperature reaction of [CrCl₃(thf)₃] with LiC₆H₃Cl₂-2,6 yields the organochromium(III) compound [Li(thf)₄][Cr^III(C₆H₃Cl₂-2,6)₄] (1) in 48% yield. The homoleptic, anionic species [Cr^III(C₆H₃Cl₂-2,6)₄]⁻ is electrochemically related to the neutral one [Cr^IV(C₆H₃Cl₂-2,6)₄] (2) through a reversible one-electron exchange process (E_1/2 = 0.16 V, ΔE_p = 0.09 V, i_pa/i_pc = 1.18). Compound 2 was isolated in 74% yield by chemical oxidation of 1 with [N(C₆H₄Br-4)₃][SbCl₆]. Attempts to prepare the salt [NBu₄][Cr^III(C₆Cl₅)₄] (4) by direct arylation of [CrCl₃(thf)₃] with LiC₆Cl₅ in the presence of [NBu₄]Br gave the organochromium(II) salt [NBu₄]₂[Cr^II(C₆Cl₅)₄] (3) instead, as the result of a reduction process. The salt [NBu₄][Cr^III(C₆Cl₅)₄] (4) was cleanly prepared by comproportionation of 3 and [Cr^IV(C₆Cl₅)₄]. The reaction of [MoCl₄(dme)] with LiC₆Cl₅ in Et₂O solution proceeded with oxidation of the metal center to give the paramagnetic (S = 1/2), five-coordinate salt [Li(thf)₄][Mo^VO(C₆Cl₅)₄] (5). The crystal and molecular structures of 1 and 2 have been established by X-ray diffraction methods. The magnetic properties of 1 and 4 (S = 3/2) as well as those of 2 (S = 1) have been established by EPR spectroscopy as well as by ac and dc magnetization measurements.     

Synthesis and characterization of three new fluorovanadate complexes: N(C2H5)4[VOF4], N(CH3)4[VOF3Cl], N(C4H9)4[VOF3Br] and theoretical calculations of VOF4, VOF3Cl and VOF3Br ions

The reaction of VOF₃ with (C₂H₅)₄NF, (CH₃)₄NCl and (C₄H₉)₄NBr salts in anhydrous CH₃CN produced new complexes with the anion general formula [VOF₃X]⁻ in that (X = F⁻, Cl⁻, Br⁻). These were characterized by elemental analysis, IR, UV/Visible and ¹⁹F NMR spectroscopy. The optimized geometries and frequencies of the stationary point are calculated at the B3LYP/6-311G level of theory. Theoretical results showed that the VX (X = F, Cl, Br) bond length values for the [VOF₃X]⁻ in compounds 1-3 are 1.8247, 2.4031 and 2.5595 Å, respectively. Also, the VF₅ bond length values in [VOF₃X]⁻ are 1.824, 1.812 and 1.802 Å, respectively. These results reveal that the bond order for VX bonds decrease from compounds 1 to 3, while for VF₅ bonds, the bond orders increase. It can be concluded that the decrease of VX bonds lengths and the increase of VF₅ bond lengths in compounds 1-3 result from the increase of the hyperconjugation from compounds 1 to 3. Harmonic vibrational frequencies and infrared intensities for VOF₄⁻, VOF₃Cl⁻ and VOF₃Br⁻ are studied by means of theoretical and experimental methods. The calculated frequencies are in reasonable agreement with the experiment values. These data can be used in models of phosphoryl transfer enzymes because vanadate can often bind to phosphoryl transfer enzymes to form a trigonal-bipyramidal structure at the active site.     

Calorimetric study and thermal analysis of [Gd4/3Y2/3(Gly)6(H2O)4](ClO4)6·5H2O and [ErY(Gly)6(H2O)4](ClO4)6·5H2O (Gly: glycin)

Two solid-state coordination compounds of rare earth metals with glycin, [Gd_4/3Y_2/3(Gly)₆(H₂O)₄](ClO₄)₆·5H₂O and [ErY(Gly)₆(H₂O)₄](ClO₄)₆·5H₂O were synthesized. The low-temperature heat capacities of the two coordination compounds were measured with an adiabatic calorimeter over the temperature range from 78 to 376 K. [Gd_4/3Y_2/3(Gly)₆(H₂O)₄](ClO₄)₆·5H₂O melted at 342.90 K, while [ErY(Gly)₆(H₂O)₄](ClO₄)₆·5H₂O melted at 328.79 K. The molar enthalpy and entropy of fusion for the two coordination compounds were determined to be 18.48 kJ mol⁻¹ and 53.9 J K⁻¹ mol⁻¹ for [Gd_4/3Y_2/3(Gly)₆(H₂O)₄](ClO₄)₆·5H₂O, 1.82 kJ mol⁻¹ and 5.5 J K⁻¹ mol⁻¹ for [ErY(Gly)₆(H₂O)₄](ClO₄)₆·5H₂O, respectively. Thermal decompositions of the two coordination compounds were studied through the thermogravimetry (TG). Possible mechanisms of the decompositions are discussed.     

Characterization of an aluminium(III)–citrate species by means of ion chromatography with inductively coupled plasma-atomic emission spectrometry detection

The aluminium(III)–citrate complex (NH₄)₄[Al₂(C₆H₄O₇)(C₆H₅O₇)₂]·4H₂O was characterized using anion exchange chromatography on-line coupled with the element specific ICP-AES detector. Time-dependent monitoring of individual species in aqueous solution at different temperatures gave information about the species stability and the decomposition pathway. The aluminium–citrate complex (NH₄)₄[Al₂(C₆H₄O₇)(C₆H₅O₇)₂]·4H₂O disintegrated via an unknown intermediary Al(III)–citrate species from which the thermodynamically stable complex [Al₃(C₆H₄O₇)₃(OH)(H₂O)]⁴⁻ was formed. The activation energy for the decomposition reaction and the pre-exponential factor were determinated to be E_a = 81.95 kJ mol⁻¹ and A = 3.62 × 10¹³ s⁻¹.     

Thermogravimetric investigation on the chloride binding behaviour of MK-lime paste

The hydration products of 2.5, 5 and 10% Cl⁻ containing metakaolin (MK)-lime pastes are compared with the same obtained from MK-lime paste to understand the chloride binding behaviour of MK during the hydration of cement. Results indicate that 2.5% Cl⁻ addition into the MK-lime paste initially enhances the formation of Friedel's salt (Ca₂Al(OH)₆Cl·2H₂O), but Friedel's salt decomposes at later stages due to the formation of stratlingite (C₂ASH₈). In 5 and 10% chloride containing pastes, Friedel's salt is observed throughout the reaction periods along with the high amount of CSH. Small amount of stratlingite is also formed on or after 60 day hydration of 5% Cl⁻ containing MK-lime pastes. On the other hand, MK-lime-10% Cl⁻ containing pastes show the complete absence of stratlingite and C₄AH₁₃ through out the hydration period, which are the major hydration products of MK-lime paste. Mesuarements of pH of the simulated pore fliuds help to understand the decomposition behaviour of Friedel's salt. From the experimental results, chloride binding mechanism of MK-lime paste is also discussed.     

Synthesis and structural aspects of M-allyl (M = Ir, Rh) complexes

The synthesis, characterization and chemistry of novel η³-allyl metal complexes (M = Ir, Rh) are described. The structures of compounds (C₅Me₄H)Ir(PPh₃)Cl₂ (1), (C₅Me₄H)Ir(PPh₃)(η³-1-methylallyl)Br (3a), (C₅Me₄H)Ir(η⁴-1,3,5-hexatriene) (8), and (C₅Me₅)Rh(η³-1-ethylallyl)Br (5d) have been determined by X-ray crystallography. Structural comparisons among these complexes are discussed. It is found that the neutral metal allylic complex [Cp^∗IrCl(η³-methylallyl)] (5) ionizes in polar solvents to give [Cp^∗Ir(η³-methylallyl)]⁺Cl⁻ (6) and reaches equilibrium (5 ? 6) at room temperature. Addition of tertiary phosphine ligands to neutral complexes such as [Cp^∗Ir(η³-methylallyl)Cl], results in the formation of stable ionic phosphine adducts. Factors such as solvent, length of carbon chain, temperature and light are discussed with respect to the formation, stability and structure of the allyl complexes.     

X-ray diffraction study of bisphosphonate metal complexes: Mg,Sr and Ba complexes of (dichloromethylene)bisphosphonic acid P,P′-dibenzoyl anhydride

The first alkaline earth metal complexes of a dibenzoyl derivative of clodronic acid were prepared and characterised by X-ray crystallography, elemental analysis and infrared spectroscopy. The complexes were [Mg{[Cl₂C(PO₂O(C(O)C₆H₅))₂](H₂O)₅} · H₂O] (1), [Sr₂{[Cl₂C(PO₂O(C(O)C₆H₅))₂]₂(H₂O)₉} · H₂O]_n (2) and [Ba{Cl₂C(PO₂O(C(O)C₆H₅))₂}(H₂O)₂]_n (3). The monomeric units of 1 and the polymeric chains of 2 and 3 form 2D layer-like structures through intermolecular hydrogen bonds. The Cl₂C(PO₂O(C(O)C₆H₅))₂²⁻ ligand acts as a bridging and chelating ligand, forming six- and eight-membered chelate rings with metal atoms. In addition, the previously determined polymeric calcium complex of clodronate, [Ca₂{Cl₂C(PO₃)₂}(H₂O)₆ · 4.5H₂O]_n(4), was synthesised by hydrolysis method from the dibenzoyl derivative of clodronic acid.     

Ni(II) and Co(II) complexes with 2,4-dichlorophenoxyacetic acid and 2-(2,4-dichlorophenoxy)-propionic acid

Nickel(II) and cobalt(II) complexes with the commercial herbicides 2,4-dichlorophenoxyacetic acid (2,4D; C₈H₆O₃Cl₂) and 2-(2,4-dichlorophenoxy)-propionic acid (2,4DP; C₉H₈O₃Cl₂) were prepared and characterized. On the basis of the results of elemental analysis and Ni and Co determination, the following molecular formulae were proposed for the obtained compounds: Ni(C₈H₅O₃Cl₂)₂·6H₂O, Co(C₈H₅O₃Cl₂)₂·6H₂O, Ni(C₉H₇O₃Cl₂)₂·2H₂O and Co(C₉H₇O₃Cl₂)₂·2H₂O. X-ray powder analysis was carried out. The IR, electronic (VIS) spectra and conductivity data were discussed. Water solubility of the synthesized complexes at room temperature was examined. Thermal decomposition of the compounds was studied. Dehydration processes occur during heating in air. The anhydrous compounds decompose via different intermediate products to oxides. TG/MS studies indicate formation of gaseous mass fragments of decomposition including H₂O⁺, OH⁺, CO₂ ⁺, HCl⁺, Cl₂ ⁺, CH₃Cl⁺, CH₂O⁺, C₆H₆ ⁺ and other. This revised version was published online in August 2006 with corrections to the Cover Date.     

Computational investigation of solvent effect on the structure,spectroscopic properties (13C, 1H NMR and IR,UV), NLO properties and HOMO–LUMO analysis of Ru(NHC)2Cl2(=CH-p-C6H5) complex

This paper presents, a theoretical study of the structural, ¹³C and ¹H NMR chemical shifts, electronic transitions, vibrational analysis, and first hyperpolarizability for Ru(NHC)₂Cl₂(=CH-p-C₆H₅) complex in gas phase and different solvents. The solvent effect on structural parameters, frontier orbital energies, Ru=C_carbene and C_carbene-H stretching frequencies, and chemical shifts of C_carbene, C_NHC and H_carbene of complex was explored based on Polarizable Continuum Model (PCM). The wavenumbers of υ(Ru=C_carbene) and υ(C_carbene-H) of complex in different solvents were correlated with the Kirkwood–Bauer–Magat equation (KBM). As well as, the polarizability and the first order hyperpolarizability values of the investigated compound were computed in various solvents.