Predicting a New Δ-Proton Sponge-Base of 4,12-Dihydrogen-4,8,12-triazatriangulene through Proton Affinity, Aromatic Stabilization Energy, and Aromatic Magnetism.

Herein, we report designing a new Δ (delta-shaped) proton sponge base of 4,12-dihydrogen-4,8,12-triazatriangulene (compound 1) and calculating its proton affinity (PA), aromatic stabilization, natural bond orbital (NBO), electron density ρ(r), Laplacian of electron density ∇2 ρ(r), (2D-3D) multidimensional off-nucleus magnetic shielding (σzz (r) and σiso (r)), and scanning nucleus-independent chemical shift (NICSzz and NICS). Density functional theory (DFT) at B3LYP/6-311+G(d,p), ωB97XD/6-311+G(d,p), and PW91/def2TZVP were used to compute the magnetic shielding variables. In addition, relevant bases like pyridine, quinoline, and acridine were also studied and compared. The protonation of compound 1 yields a highly symmetric carbocation of three Hückel benzenic rings. Comparing our findings of the studied molecules showed that compound 1 precedes others in PA, aromatic isomerization stabilization energy, and basicity. Therefore, the basicity may be enhanced when a conjugate acid gains higher aromatic features than its unprotonated base. Both multidimensional σzz (r) and σiso (r) off-nucleus magnetic shieldings outperformed electron-based techniques and can visually monitor changes in aromaticity that occur by protonation. The B3LYP/6-311+G(d,p), ωB97XD/6-311+G(d,p), and PW91/def2TZVP levels showed no significant differences in detailing isochemical shielding surfaces.

A Personal Account on Inorganic Reaction Mechanisms.

The presented Review is focused on the latest research in the field of inorganic chemistry performed by the van Eldik group and his collaborators. The first part of the manuscript concentrates on the interaction of nitric oxide and its derivatives with biologically important compounds. We summarized mechanistic information on the interaction between model porphyrin systems (microperoxidase) and NO as well as the recent studies on the formation of nitrosylcobalamin (CblNO). The following sections cover the characterization of the Ru(II)/Ru(III) mixed-valence ion-pair complexes, including Ru(II)/Ru(III)(edta) complexes. The last part concerns the latest mechanistic information on the DFT techniques applications. Each section presents the most important results with the mechanistic interpretations.

Selective Noble Gas Inclusion in Pentagon-Dodecahedral X20-Cages.

Using DFT-based computational chemistry calculations (ωB97XD/def2-tzvp//ωB97XD/def2-svp/svpfit + ZPE(ωB97XD/def2-svp/svpfit)), binding energies of noble gases encapsulated in a series of dodecahedrane molecules (general formula: X20H20 where X = C, Si, Ge, Sn and Pb, and X20 where X = N, P, As, Sb and Bi) were calculated to learn about the noble gas selectivity. Based on calculated binding energies, the Sn20H20 cage can best accommodate noble gases with a medium size radius (Ar and Kr), while the Pb20H20 dodecahedrane cage is best suited for noble gases with the larger radii (Xe and Rn). On the other hand, from the elements of the V main group of the periodic table, the Bi20 cage has shown the best results to selectively encapsulate Ar and Kr, with the amounts of energy being released being -5.24 kcal/mol and -6.13 kcal/mol, respectively. By monitoring the geometric changes of all here-reported host cages upon encapsulating the noble gas guest, the host has shown minor to no flexibility, testifying to the high rigidity of the dodecahedrane structure which was further reflected in very high encapsulating energies.

Investigation of water substitution at RuII complexes by conceptual density function theory approach.

In this paper, we investigated water exchange reactions and substitution of aqua RuII complexes of general formula [Ru(terpy)(N^N)(H2 O)]2+ (where N^N = ethylenediamine (en), 1,2-(aminomethyl)pyridine (ampy) and 2,2'-bipyridine (bipy)) by ammonia and thioformaldehyde. These reactions were studied in detail by applying conceptual density functional theory. This approach enabled us to gain further insight into the underlying reaction mechanism at the microscopic level (involving only direct participants of the reaction, without the influence of the solvent) and to put the concept of reaction mechanism on a quantitative basis. The course of the chemical reaction along the reaction coordinate ξ, is rationalized in terms of reaction energy, force, dipole moment, and reaction electronic flux (REF). The results yield and characterize the significant influence of an intermolecular hydrogen bond formed between the entering and the spectator ligand to the overall energy barrier of the reactions.

Dimorpholinoacetylene and Its Use for the Synthesis of Tetraaminocyclobutadiene Species.

The new diaminoacetylene (DAA) dimorpholinoacetylene (3) was prepared from 1,1-dimorpholinoethene (1) by bromination to form the dibromoketene aminal 2, which upon lithiation afforded 3 through a Fritsch-Buttenberg-Wiechell rearrangement. Heating 3 at elevated temperatures resulted in a complete conversion into the dimer 1,1,2,4-tetramorpholino-1-buten-3-yne (4), which was used for the synthesis of four-membered cyclic bent allene (CBA) transition-metal complexes of the type [(CBA)MLn ] (5-7; MLn =AuCl, RhCl(COD), RhCl(CO)2 ; CBA=1,3,4,4-tetramorpholino-1,2-cyclobutadiene; COD=1,5-cyclooctadiene). The reaction of 3 with tetraethylammonium bromide gave 1,2,3,4-tetramorpholinocyclobutenylium bromide (8), which reacted with bromine to form 1,2,3,4-tetra(morpholino)cyclobutenediylium bis(tribromide) (9). Compound 9 represents the first fully characterized compound containing a tetraaminocyclobutadiene dication and displays a nearly planar C4 N4 core as shown by X-ray diffraction analysis. Detailed quantum chemical calculations were performed to assess the aromaticity of tetraaminocyclubutadiene dications by employing the Nucleus Independent Chemical Shift (NICS) method and current density analysis.

Synthesis of Camphor-Derived Bis(pyrazolylpyridine) Rhodium(III) Complexes: Structure-Reactivity Relationships and Biological Activity.

Two novel rhodium(III) complexes, namely, [RhIII(X)Cl3] (X = 2 2,6-bis((4 S,7 R)-7,8,8-trimethyl-4,5,6,7-tetrahydro-1 H-4,7-methanoindazol-3-yl)pyridine or 2,6-bis((4 S,7 R)-1,7,8,8-tetramethyl-4,5,6,7-tetrahydro-1 H-4,7-methanoindazol-3-yl)pyridine), were synthesized from camphor derivatives of a bis(pyrazolylpyridine), tridentate nitrogen-donor chelate system, giving [RhIII(H2L*)Cl3] (1a) and [RhIII(Me2L*)Cl3] (1b). A rhodium(III) terpyridine (terpy) ligand complex, [RhIII(terpy)Cl3] (1c), was also synthesized. By single-crystal X-ray analysis, 1b crystallizes in an orthorhombic P212121 system, with two molecules in the asymmetric unit. Tridentate coordination by the N,N,N-donor localizes the central nitrogen atom close to the rhodium(III) center. Compounds 1a and 1b were reactive toward l-methionine (l-Met), guanosine-5'-monophosphate (5'-GMP), and glutathione (GSH), with an order of reactivity of 5'-GMP > GSH > l-Met. The order of reactivity of the RhIII complexes was: 1b> 1a > 1c. The RhIII complexes showed affinity for calf thymus DNA and bovine serum albumin by UV-vis and emission spectral studies. Furthermore, 1b showed significant in vitro cytotoxicity against human epithelial colorectal carcinoma cells. Since the RhIII complexes have similar coordination modes, stability differences were evaluated by density functional theory (DFT) calculations (B3LYP(CPCM)/LANL2DZp). With (H2L*) and (terpy) as model ligands, DFT calculations suggest that both tridentate ligand systems have similar stability. In addition, molecular docking suggests that all test compounds have affinity for the minor groove of DNA, while 1b and 1c have potential for DNA intercalation.

Switching between Inner- and Outer-Sphere PCET Mechanisms of Small-Molecule Activation: Superoxide Dismutation and Oxygen/Superoxide Reduction Reactivity Deriving from the Same Manganese Complex.

Readily exchangeable water molecules are commonly found in the active sites of oxidoreductases, yet the overwhelming majority of studies on small-molecule mimics of these enzymes entirely ignores the contribution of water to the reactivity. Studies of how these enzymes can continue to function in spite of the presence of highly oxidizing species are likewise limited. The mononuclear MnII complex with the potentially hexadentate ligand N-(2-hydroxy-5-methylbenzyl)-N,N',N'-tris(2-pyridinylmethyl)-1,2-ethanediamine (LOH) was previously found to act as both a H2O2-responsive MRI contrast agent and a mimic of superoxide dismutase (SOD). Here, we studied this complex in aqueous solutions at different pH values in order to determine its (i) acid-base equilibria, (ii) coordination equilibria, (iii) substitution lability and operative mechanisms for water exchange, (iv) redox behavior and ability to participate in proton-coupled electron transfer (PCET) reactions, (v) SOD activity and reductive activity toward both oxygen and superoxide, and (vi) mechanism for its transformation into the binuclear MnII complex with (H)OL-LOH and its hydroxylated derivatives. The conclusions drawn from potentiometric titrations, low-temperature mass spectrometry, temperature- and pressure-dependent 17O NMR spectroscopy, electrochemistry, stopped-flow kinetic analyses, and EPR measurements were supported by the structural characterization and quantum chemical analysis of proposed intermediate species. These comprehensive studies enabled us to determine how transiently bound water molecules impact the rate and mechanism of SOD catalysis. Metal-bound water molecules facilitate the PCET necessary for outer-sphere SOD activity. The absence of the water ligand, conversely, enables the inner-sphere reduction of both superoxide and dioxygen. The LOH complex maintains its SOD activity in the presence of •OH and MnIV-oxo species by channeling these oxidants toward the synthesis of a functionally equivalent binuclear MnII species.

Redox Behavior of a Dinuclear Ruthenium(II) Complex Bearing an Uncommon Bridging Ligand: Insights from High-Pressure Electrochemistry.

A dinuclear ruthenium complex bridged by 2,3,5,6-pyrazinetetracarboxylic acid (µ-LH22-) was synthesized and characterized by X-ray crystallography, cyclic voltammetry under ambient and elevated pressures, electron paramagnetic resonance (EPR) and UV/vis-NIR (NIR = near-infrared) spectroelectrochemistry, pulse radiolysis, and computational methods. We probed for the first time in the field of mixed-valency the use of high-pressure electrochemical methods. The investigations were directed toward the influence of the protonation state of the bridging ligand on the electronic communication between the ruthenium ions, since such behavior is interesting in terms of modulating redox chemistry by pH. Starting from the [RuII(µ-LH22-)RuII]0 configuration, which shows an intense metal-to-ligand charge transfer absorption band at 600 nm, cyclic voltammetry revealed a pH-independent, reversible one-electron reduction and a protonation-state-dependent (proton coupled electron transfer, PCET) reversible oxidation. Deeper insight into the electrode reactions was provided by pressure-dependent cyclic voltammetry up to 150 MPa, providing insight into the conformational changes, the protonation state, and the environment of the molecule during the redox processes. Spectroelectrochemical investigations (EPR, UV/vis-NIR) of the respective redox reactions suggest a ligand-centered radical anion [RuII(µ-LH2•3-)RuII]- upon reduction (EPR Δg = 0.042) and an ambiguous, EPR-silent one-electron oxidized state. In both cases, the absence of the otherwise typical broad intervalence charge transfer bands in the NIR region for mixed-valent complexes support the formulation as radical anionic bridged compound. However, on the basis of high-pressure electrochemical data and density functional theory calculations the one-electron oxidized form could be assigned as a charge-delocalized [RuII.5(µ-LH22-)RuII.5]+ valence tautomer rather than [RuIII(µ-LH2•3-)RuIII]+. Deprotonation of the bridging ligand causes a severe shift of the redox potential for the metal-based oxidation toward lower potentials, yielding the charge-localized [RuIII(µ-LH3-)RuII]0 complex. This PCET process is accompanied by large intrinsic volume changes. All findings are supported by computational methods (geometry optimization, spin population analysis). For all redox processes, valence alternatives are discussed.

Adaptive Behavior of Dynamic Orthoester Cryptands.

The integration of dynamic covalent bonds into macrocycles has been a tremendously successful strategy for investigating noncovalent interactions and identifying effective host-guest pairs. While numerous studies have focused on the dynamic responses of macrocycles and larger cages to various guests, the corresponding constitutionally dynamic chemistry of cryptands remains unexplored. Reported here is that cryptands based on orthoester bridgeheads offer an elegant entry to experiments in which a metal ion selects its preferred host from a dynamic mixture of competing subcomponents. In such dynamic mixtures, the alkali metal ions Li+ , Na+ , K+ , Rb+ , and Cs+ exhibit pronounced preferences for the formation of cryptands of certain sizes and donor numbers, and the selection is rationalized by DFT calculations. Reported is also the first self-assembly of a chiral orthoester cryptate and a preliminary study on the use of stereoisomers as subcomponents.

A Soft Grip: Magnesium Complexes with a Phosphine-Modified Phosphonium Diylidic Lewis Base.

Simple strategies to obtain magnesium complexes with the soft chelating diylidic ligand [Ph2 PCHPPh2 (fluorenylidene)]- (dppmflu- ) were developed to evaluate the influence of the hard acid (cation) and soft base (anion) mismatch on the stability and reactivity of the formed derivatives. Deprotonation of the precursor Ph2 PCH2 PPh2 (flu) (dppmfluH) by an alkylmagnesium derivative or magnesium amide provided access to [{Mg(dppmflu)(µ-nBu)}2 ], [Mg(dppmflu){N(SiMe3 )2 }], and [{Mg(dppmflu)(µ-Me)}2 ], which were used as starting materials for further investigations. The reaction of [{Mg(dppmflu)(µ-nBu)}2 ] with PhSiH3 in the presence of THF allowed isolation of the magnesium hydride complex [{Mg(dppmflu)(µ-H)(thf)}2 ] without a stabilizing nitrogen donor ligand. Prolonged heating enforced ligand redistribution and [{Mg(dppmflu)(µ-H)(thf)}2 ] was converted to [Mg(dppmflu)2 ] and MgH2 . The homoleptic derivative [Mg(dppmflu)2 ], in which the magnesium center is in a very soft ligand environment, can open a THF molecule by frustrated Lewis pair reactivity to give [{Mg(dppmflu)(µ-OC4 H8 dppmflu)}2 ].

Studies on the Reaction of Iron(II) with NO in a Noncoordinating Ionic Liquid.

In an earlier study we investigated the reaction of iron(II) chloride with NO in a strongly coordinating ionic liquid 1-ethyl-3-methylimidazolium dicyanamide [emim][dca] and showed that the actual reactive species in solution was [Fe(II)(dca)5Cl](4-). For the present report we investigated in detail how this reaction could proceed in a noncoordinating ionic liquid 1-ethyl-3-methylimidazolium trifluoromethylsulfonate [emim][OTf]. The donor ability of OTf(-) is much lower than that of dca(-), such that the solubility of FeCl2 in [emim][OTf] strongly depended on other donors like water or chloride ions present or added to the ionic liquid. On increasing the chloride concentration in [emim][OTf], the tetrachloridoferrate complex [emim]2[FeCl4] was formed, as verified by X-ray crystallography. This complex undergoes reversible binding of NO, for which the UV-vis spectral characteristics of the green-brown nitrosyl product resembled that found for the corresponding nitrosyl complexes formed in water and [emim][dca] as solvents. A detailed analysis of the spectra revealed that the {Fe-NO}(7) species has Fe(II)-NO(•) character in contrast to Fe(III)-NO(-) as found for the other solvents. The formation constant, however, is much higher than in [emim][dca], lying closer to the value found for water as solvent. Surprisingly, the Mössbauer spectrum found in [emim][OTf] is very unusual and unsimilar to that found in water and [emim][dca] as solvents, pointing at a different electron density distribution between Fe and NO in {Fe-NO}.7 First, the high isomer shift points to the presence of iron(II) species in solution, thus indicating that upon NO binding no oxidation to iron(III) occurs. Second, the negligible quadrupole splitting suggests a high local symmetry around the iron center. The nitrosyl product is suggested to be [Fe(II)Cl3NO](-), which is supported by electron paramagnetic resonance (EPR) and IR measurements. The nature of the Fe(II) complexes formed in [emim][OTf] depends on the additives required to dissolve FeCl2 in this ionic liquid.

Preparation of candidate reference materials for the determination of phosphorus containing flame retardants in styrene-based polymers.

Candidate reference materials (RM) for the analysis of phosphorus-based flame retardants in styrene-based polymers were prepared using a self-made mini-extruder. Due to legal requirements of the current restriction for the use of certain hazardous substances in electrical and electronic equipment, focus now is placed on phosphorus-based flame retardants instead of the brominated kind. Newly developed analytical methods for the first-mentioned substances also require RMs similar to industrial samples for validation and verification purposes. Hence, the prepared candidate RMs contained resorcinol-bis-(diphenyl phosphate), bisphenol A bis(diphenyl phosphate), triphenyl phosphate and triphenyl phosphine oxide as phosphorus-based flame retardants. Blends of polycarbonate and acrylonitrile-co-butadiene-co-styrene as well as blends of high-impact polystyrene and polyphenylene oxide were chosen as carrier polymers. Homogeneity and thermal stability of the candidate RMs were investigated. Results showed that the candidate RMs were comparable to the available industrial materials. Measurements by ICP/OES, FTIR and NMR confirmed the expected concentrations of the flame retardants and proved that analyte loss and degradation, respectively, was below the uncertainty of measurement during the extrusion process. Thus, the candidate RMs were found to be suitable for laboratory use.

Behavior of highly diluted electrolytes in strong electric fields-prevention of alumina deposition on grading electrodes in HVDC transmission modules by CO2-induced pH-control.

Alumina deposition on platinum grading electrodes in high voltage direct current (HVDC) transmission modules is an unsolved problem that has been around for more than three decades. This is due to the unavoidable corrosion of aluminum heat sinks that causes severe damage to electrical power plants and losses in the range of a million Euro range per day in power outage. Simple experiments in a representative HV test setup showed that aluminates at concentrations even below 10(-8) mol L(-1) can deposit on anodes through neutralization by protons produced in de-ionized water (κ≤0.15 µS cm(-1)) at 20-35 kV (8 mA) per electrode. In this otherwise electrolyte-poor aqueous environment, the depositions are formed three orders of magnitude below the critical precipitation concentration at pH 7! In the presence of an inert electrolyte such as TMAT (tetramethylammonium-p-toluenesulfonate), at a concentration level just above that of the total dissolved aluminum, no deposition was observed. Deposition can be also prevented by doping with CO2 gas at a concentration level that is magnitudes lower than that of the dissolved aluminum. From an overview of aqueous aluminum chemistry, the mystery of the alumina deposition process and its inhibition by CO2 is experimentally resolved and fully explained by field accumulation and repulsion models in synergism with acid-base equilibria. The extraordinary size of the alumina depositions is accounted for in terms of proton tunneling through "hydrated" alumina, which is supported by quantum chemical calculations. As a consequence, pulse-purging with pure CO2 gas is presented as a technical solution to prevent the deposition of alumina.

Coordination of terpyridine to Li+ in two different ionic liquids.

On the basis of (7)Li NMR experiments, the complex-formation reaction between Li(+) and the tridentate N-donor ligand terpyridine was studied in the ionic liquids [emim][NTf2] and [emim][ClO4] as solvents. For both ionic liquids, the NMR data implicate the formation of [Li(terpy)2](+). Density functional theory calculations show that partial coordination of terpyridine involving the coordination of a solvent anion can be excluded. In contrast to the studies in solution, X-ray diffraction measurements led to completely different results. In the case of [emim][NTf2], the polymeric lithium species [Li(terpy)(NTf2)]n was found to control the stacking of this complex, whereas crystals grown from [emim][ClO4] exhibit the discrete dimeric species [Li(terpy)(ClO4)]2. However, both structures indicate that each lithium ion is formally coordinated by one terpy molecule and one solvent anion in the solid state, suggesting that charge neutralization and π stacking mainly control the crystallization process.

Host-guest complexes of mixed glycol-bipyridine cryptands: prediction of ion selectivity by quantum chemical calculations, part V.

The selectivity of the cryptands [2.2.bpy] and [2.bpy.bpy] for the endohedral complexation of alkali, alkaline-earth and earth metal ions was predicted on the basis of the DFT (B3LYP/LANL2DZp) calculated structures and complex-formation energies. The cavity size in both cryptands lay between that for [2.2.2] and [bpy.bpy.bpy], such that the complexation of K(+), Sr(2+) and Tl(3+) is most favorable. While the [2.2.bpy] is moderately larger, preferring Rb(+) complexation and demonstrating equal priority for Sr(2+) and Ba(2+), the slightly smaller [2.bpy.bpy] yields more stable cryptates with Na(+) and Ca(2+). Although the CH2-units containing molecular bars fixed at the bridgehead nitrogen atoms determine the flexibility of the cryptands, the twist angles associated with the bipyridine and glycol building blocks also contribute considerably.

Ligand exchange at tetra-coordinated beryllium centres.

Mono and dinuclear phosphine complexes of beryllium halides [(PMe3)2BeX2], [(PMe3)BeX2]2 and [(PCy3)BeX2]2 (X = Cl, Br, I) were synthesised and characterised via NMR and IR spectroscopy as well as single crystal X-ray diffraction experiments. Dissociation and ligand exchange processes at these complexes were investigated through variable temperature NMR experiments in combination with line shape analysis and complemented by quantum chemical calculations. The PMe3 dissociation energy is smallest in [(PMe3)2BeCl2], while PMe3 exchange is similar in energy in all mononuclear [(PMe3)2BeX2] complexes and follows an interchange mechanism. While [(PMe3)BeX2]2 dissociates homolytically, [(PCy3)BeX2]2 cleaves one phosphine ligand. These distinctive dissociation processes account for the different chemical behaviour of these complexes.

Gutmann donor and acceptor numbers for ionic liquids.

We present for the first time Gutmann donor and acceptor numbers for a series of 36 different ionic liquids that include 26 distinct anions. The donor numbers were obtained by (23)Na NMR spectroscopy and show a strong dependence on the anionic component of the ionic liquid. The donor numbers measured vary from -12.3 kcal mol(-1) for the ionic liquid containing the weakest coordinative anion [emim][FAP] (1-ethyl-3-methylimidazolium tris(pentafluoroethyl)trifluorophosphate), which is a weaker donor than 1,2-dichloroethane, to 76.7 kcal mol(-1) found for the ionic liquid [emim][Br], which exhibits a coordinative strength in the range of tertiary amines. The acceptor numbers were measured by using (31)P NMR spectroscopy and also vary as a function of the anionic and cationic component of the ionic liquid. The data are presented and correlated with other solvent parameters like the Kamlet-Taft set of parameters, and compared to the donor numbers reported by other groups.

Role of π-acceptor effects in controlling the lability of novel monofunctional Pt(II) and Pd(II) complexes: crystal structure of [Pt(tripyridinedimethane)Cl]Cl.

The kinetics and mechanism of substitution reactions of novel monofunctional [Pt(tpdm)Cl](+) and [Pd(tpdm)Cl](+) complexes (where tpdm = tripyridinedimethane) and their aqua analogues with thiourea (tu), L-methionine (L-met), glutathione (GSH), and guanosine-5'-monophosphate (5'-GMP) were studied in 0.1 M NaClO(4) at pH = 2.5 (in the presence of 10 mM NaCl for reactions of the chlorido complexes). The reactivity of the investigated nucleophiles follows the order tu > l-met > GSH > 5'-GMP. The reported rate constants showed the higher reactivity of the Pd(II) complexes as well as the higher reactivity of the aqua complex than the corresponding chlorido complex. The negative values reported for the activation entropy as well as the activation volume confirmed an associative substitution mode. In addition, the molecular and crystal structure of [Pt(tpdm)Cl]Cl was determined by X-ray crystallography. The compound crystallizes in a monoclinic space group C2/c with two independent molecules of the complex and unit cell dimensions of a = 38.303(2) Å, b = 9.2555(5) Å, c = 27.586(2) Å, ß = 133.573(1)°, and V = 7058.3(8) Å(3). The cationic complex [Pt(tpdm)Cl](+) exhibits square-planar coordination around the Pt(II) center. The lability of the [Pt(tpdm)Cl](+) complex is orders of magnitude lower than that of [Pt(terpyridine)Cl](+). Quantum chemical calculations were performed on the [Pt(tpdm)Cl](+) and [Pt(terpyridine)Cl](+) complexes and their reactions with thiourea. Theoretical computations for the corresponding Ni(II) complexes clearly demonstrated that π-back-bonding properties of the terpyridine chelate can account for acceleration of the nucleophilic substitution process as compared to the tpdm chelate, where introduction of two methylene groups prevents such an effective π-back bonding.

Kinetic and mechanistic studies of base-catalyzed phenylselenoetherification of (Z)- and (E)-hex-4-en-1-ols.

The mechanism of phenylselenoetherification of (Z)- and (E)-hex-4-en-1-ols using some bases (triethylamine, pyridine, quinoline, 2,2'-bipyridine) as catalysts and some solvents [tetrahydrofuran (THF) and CCl4] as reaction media was examined through studies of kinetics of the cyclization by UV-vis spectrophotometry. It was demonstrated that the intramolecular cyclization is facilitated in the presence of bases as a result of the hydrogen bond between the base and the alkenol's OH group. The rate constants in the base-catalyzed reactions are remarkably influenced by the bulkiness and basicity of the base used and the nature of the considered nitrogen donors. The obtained values for rate constants show that the reaction with triethylamine is the fastest one. THF with higher polarity and higher basic character is better as a solvent than CCl4. Quantum-chemical calculations [MP2(fc)/6-311+G**//B3LYP/6-311+G** + ZPE(B3LYP/6-311+G**] show that the cyclization of (Z)-hex-4-en-1-ol to a tetrahydrofuranoid five-membered ring is kinetically controlled, while the cyclization of (E)-hex-4-en-1-ol to the tetrahydropyranoid six-membered ring is thermodynamically controlled. This is in accordance with previous experimental findings.

Novel dinuclear platinum(II) complexes containing mixed nitrogen-sulfur donor ligands.

A series of novel dinuclear platinum(II) complexes were synthesized containing a mixed nitrogen-sulfur donor bidentate chelate system in which the two platinum centers are connected by an aliphatic chain of variable length. The bidentate chelating ligands were selected to stabilize the complex toward decomposition. The pK(a) values and reactivity of the four synthesized complexes, namely, [Pt(2)(S(1),S(4)-bis(2-pyridylmethyl)-1,4-butanedithioether)(OH(2))(4)](4+) (4NSpy), [Pt(2)(S(1),S(6)-bis(2-pyridylmethyl)-1,6-hexanedithioether)(OH(2))(4)](4+) (6NSpy), [Pt(2)(S(1),S(8)-bis(2-pyridylmethyl)-1,8-octanedithioether)(OH(2))(4)](4+) (8NSpy), and [Pt(2)(S(1),S(10)-bis(2-pyridylmethyl)-1,10-decanedithioether)(OH(2))(4)](4+) (10NSpy), were investigated. This system is of special interest because only little is known about the substitution behavior of dinuclear platinum complexes that contain a bidentate chelate that forms part of the aliphatic bridging ligand. Moreover, the ligands as well as the dinuclear complexes were examined in terms of their cytotoxic activity, and the 10NSpy complex was found to be active. Spectrophotometric acid-base titrations were performed to determine the pK(a) values of all the coordinated water molecules. The substitution of coordinated water by thiourea was studied under pseudo-first-order conditions as a function of nucleophile concentration, temperature, and pressure, using stopped-flow techniques and UV-vis spectroscopy. The results for the dinuclear complexes were compared to those for the corresponding mononuclear reference complex [Pt(methylthiomethylpyridine)(OH(2))(2)](2+) (Pt(mtp)), by which the effect of the increasing aliphatic chain length of the bridged complexes could be investigated. The results indicate that there is a clear interaction between the two platinum centers, which becomes weaker as the chain length between the metal centers increases. Furthermore, differences and similarities of the N,S-system were compared to the corresponding dinuclear N,N-system studied previously in our group. In addition, quantum chemical calculations were performed to support the interpretation and discussion of the experimental data.