Synthesis and characterization of cationic tungsten(V) methylidynes

Cationic tungsten(V) methylidynes [L4W(X)[triple bond]CH]+[B(C6F5)4]- [L = PMe3, 0.5dmpe (dmpe = Me2PCH2CH2PMe2), X = Cl, OSO2CF3] have been prepared in high yield by a one-electron oxidation of the neutral tungsten(IV) methylidynes L4W(X)[triple bond]CH with [Ph3C]+[B(C6F5)4]-. The ease and reversibility of the one-electron oxidation of L4W(X)[triple bond]CH were demonstrated by cyclic voltammetry in tetrahydrofuran (E1/2 is approximately -0.68 to -0.91 V vs Fc). The paramagnetic d1 (S = 1/2) complexes were characterized in solution by electron spin resonance (g = 2.023-2.048, quintets due to coupling to 31P) and NMR spectroscopy and Evans magnetic susceptibility measurements (mu = 2.0-2.1 muB). Single-crystal X-ray diffraction showed that the cationic methylidynes are structurally similar to the neutral precursor methylidynes. In addition, the neutral (PMe3)4W(Cl)[triple bond]CH was deprotonated with a strong base at the trimethylphosphine ligand to afford (PMe3)3(Me2PCH2)W[triple bond]CH, a tungsten(IV) methylidyne complex that features a (dimethylphosphino)methyl ligand.     

The short N [bond] F bond in N(2)F(+) and how Pauli repulsion influences bond lengths. Theoretical study of N(2)X(+), NF(3)X(+), and NH(3)X(+) (X [double bond] F, H)

Exceptionally short N [bond] F bond distances of only 1.217 A (crystal) and 1.246 A (gas phase) have been reported for N(2)F(+), making it the shortest N [bond] F bond ever observed. To trace the origin of this structural phenomenon, we have analyzed the model systems N(2)X(+), NF(3)X(+), and NH(3)X(+) (X [double bond] F, H) using generalized gradient approximation density functional theory at BP86/TZ2P. In good agreement with experiment, the computations yield an extremely short N [bond] F bond for N(2)F(+): we find N [bond] F bond distances in N(2)F(+), NF(4)(+), and NH(3)F(+) of 1.245, 1.339, and 1.375 A, respectively. The N [bond] X bonding mechanisms are quantitatively analyzed in the framework of Kohn-Sham MO theory. At variance with the current hypothesis, reduced steric and other Pauli repulsion (of substituents or lone pairs at N with F) rather than the extent of s [bond] p hybridization of N (i.e., sp versus sp(3)) are responsible for the much shorter N [bond] F distance in N(2)F(+) compared to NF(4)(+). The results for our nitrogen compounds are furthermore discussed in the more general context of how bond lengths are determined by both bonding and repulsive orbital interactions.     

A series of complexes of the phosphorus-based TTF ligand o-P2 with the metal ions Fe(II), Co(II), Ni(II), Pd(II), Pt(II), and Ag(I)

Reactions of 3,4-dimethyl-3',4'-bis(diphenylphosphino)tetrathiafulvalene, o-P2, with [BF(4)](-) salts of Fe(ii), Co(ii), Ni(II), Pd(II), and Pt(II) yield complexes of general formula [M(o-P2)(2)][BF(4)](2). Similar reactions between o-P2 and AgSbF(6) or AgPF(6) produced the salts [Ag(o-P2)(2)][X] where X = [SbF(6)](-) or [PF(6)](-). The resulting compounds were fully characterized by (1)H and (31)P{(1)H} NMR, infrared and electronic absorption spectroscopies, cyclic voltammetry, FAB-MS and single-crystal X-ray diffraction. The paramagnetic Co(II) compound exhibits an S = 3/2 state with large spin-orbit coupling contribution at higher temperatures and an effective S' = 1/2 state below 20 K. Electrochemical studies of the compounds indicate that the two functionalized TTF ligands are not in electronic communication and that they essentially behave as isolated redox centers.     

The solid-state electrochemistry of metal octacyanomolybdates,octacyanotungstates, and hexacyanoferrates explained on the basis of dissolution and reprecipitation reactions,lattice structures,and crystallinities

The electrochemical behavior of solid microparticles of metal (Ag+, Cd2+, Co2+, Cr2+, Cu2+, Fe2+, Mn2+, Ni2+, Pb2+, and Zn2+) octacyanomolybdates, octacyanotungstates, and hexacyanoferrates has been studied by voltammetry, electrochemical quartz crystal microbalance, and microscopic diffuse reflectance spectroelectrochemical measurements. The solid microparticles have been immobilized on the surface of graphite electrodes prior to the electrochemical measurements. A comparative study of the cyclic oxidation and reduction of these compounds in the presence of potassium ions revealed that any interpretation of the electrochemistry requires the solubility equilibria of the reduced compounds to be taken into account, such as in the case of the silver salts [Ag3K[X]] and [Ag4[X]] (with X = FeII(CN)6(4-), MIV(CN)8(4-) (M = Mo, W)). Because [Ag4[X]] has a lower solubility than [Ag3K[X]], the electrochemistry is accompanied by a conversion of solid [Ag3K[X]] into solid [Ag4[X]]. Two distinct voltammetric signal systems are generated by these two compounds according to [Ag3K[X]] reversible [Ag3[X]] + K(+) + e- and [Ag4[X]] reversible [Ag3[X]] + Ag(+) + e-. When silver ions are present in the solution adjacent to the microparticles, the silver octacyanometalates and silver hexacyanoferrate show a chemically reversible and very stable voltammetric behavior. Despite the fact that the electrochemistry is based upon a single-electron/single-ion transfer reaction ([Ag4[X]] reversible [Ag3[X]] + Ag(+) + e-), more than one electrochemical signal is observed because of the simultaneous presence of amorphous and crystalline particles. This study shows that the interplay of solubility equilibria and electrochemical equilibria is generally observed for the other metal octacyanomolybdates, octacyanotungstates, and hexacyanoferrates as well.     

Synthetic procedure to pyrido[2,1-f][1,2,4]triazinium salt and related compounds

N-aminopyridyl ketone salts were reacted with formamide to yield heteroaromatic pyrido[2,1-f][1,2,4]triazinium salts. Upon storage of these products in the presence of water, formation of covalent hydrates have been observed. Reaction of the same starting compound with urethane yielded 3-chloropyrido[2,1-f][1,2,4]triazinium salt which readily reacted with secondary amines to afford 3-amino derivatives. An analogous ring closure reaction of 2-formylaminomethyl- and formaminobenzylpyridine allowed the synthesis of the partially reduced 3,4-dihydropyrido[2,1-f][1,2,4]triazinium compounds. The cyclization procedure was also applied for the synthesis of the related pyrimido[2,1-f][1,2,4]triazinium salt.     

On the stability of an unsupported mercury-mercury bond linking group 15 Zintl clusters

The dimeric Zintl ion [Hg(2)(As(7))(2)](4-) has been synthesized with high crystalline yield from the reaction of an ethylendiamine solution of the intermetallic Zintl phase K(3)As(7) with diphenyl mercury. Single crystal X-ray diffraction of [K(2,2,2-crypt)](4)[Hg(2)As(14)], 1 (2,2,2-crypt = 4,7,13,16,21,24-hexaoxa-1,10-diazabicyclo[8.8.8]-hexacosane), reveals that the cluster anion exhibits a Hg-Hg bond and the compound has been further characterized using Raman spectroscopy, cyclic voltammetry and its band gap energy was measured. Theoretical studies provide a microscopic understanding of the bonding in this unusual compound.     

A Novel Cobalt(III) Mixed-polypyridyl Complex: Synthesis, Characterization and DNA Binding

ＩｎｔｒｏｄｕｃｔｉｏｎＴｈｅｔｒａｎｓｉｔｉｏｎｍｅｔａｌｐｏｌｙｐｙｒｉｄｙｌｃｏｏｒｄｉｎａｔｉｏｎｃｏｍ ｐｏｕｎｄｓａｓｔｈｅｐｒｏｂｅｏｆＤＮＡｓｔｒｕｃｔｕｒｅａｎｄｃｏｎｆｉｇｕｒａｔｉｏｎｈａｖｅｂｅｅｎｅｘｔｅｎｓｉｖｅｌｙｓｔｕｄｉｅｄｉｎｔｈｅｐａｓｔｆｅｗｙｅａｒｓ .ＴｈｅｙｉｎｔｅｒａｃｔｅｆｆｅｃｔｉｖｅｌｙｗｉｔｈＤＮＡｂｙｃｈａｎｇｉｎｇｔｈｅｔｙｐｅｏｆｈｅｔ ｅｒｏａｒｏｍａｔｉｃｌｉｇａｎｄｏｒｍｅｔａｌｃｅｎｔｅｒ.Ｔｈｏｓｅｗｉｔｈｐｈｅｎ(ｐｈｅｎａｎｅ…     

Binding studies of DNA with Co(Ⅲ) coordination compound

The binding of Co(bpy)2dppz3+ to calf thymus DNA was investigated by using absorption and emission spectroscopy,DNA melting techniques,cyclic voltammetry,viscosity and electro-phoresis measurements,where bpy is 2,2'-bipyridyl,dppz is dipyrido[3,2-o:2',3'-c] phenazine.The binding compound shows absorption hypochromicity,fluorescence enhancement,and increasing of DNA melting temperature and the specific viscosity.CV measurement shows the shifts in oxidation-reduction potential and change in peak current with addition of DNA.The compound is also shown to be more efficient photosensitisers for strand breaks in plasmid DNA.     

New synthesis, properties, and oxidizing ability of 1,3-dimethyl-5,10-methanocycloundeca[4,5]furo[2,3-d]pyrimidin- 2,4(1,3H)-dionylium tetrafluoroborate

A novel synthesis of 1,3-dimethyl-5,10-methanocycloundeca[4,5]furo[2,3-d]pyrimidin-2,4(1,3H)-dionylium tetrafluoroborate (10(+).BF(4)(-)) was accomplished by the reaction of 3,8-methano[11]annulenone with dimethylbarbituric acid and following acidic cyclization, albeit in low yield. Remarkable structural characteristics were suggested on inspection of the spectral data and MO calculation, and it was clarified that the positive charge is largely localized at the C11. The pK(R+) value of cation 10(+) was determined spectrophotometrically to be 4.6, which is much smaller by 4.1 pH unit than that of 1,3-dimethyl-7,12-methanocycloundeca[4,5]furo[2,3-d]pyrimidin-2,4(1,3H)-dionylium tetrafluoroborate (pK(R+) = 8.7). This value is also smaller by 1.6 pH unit than that of the parent 1,6-methano[11]annulenylium ion (pK(R+) = 6.2). The feature is rationalized on the basis of the perturbation derived from the bond fixation of the parent cation. The electrochemical reduction of 10(+) exhibited less negative reduction potential at -0.39 (V vs Ag/AgNO(3)) upon cyclic voltammetry (CV). In a search for reactivity, reactions of 10(+) with some nucleophiles, hydride and diethylamine, were carried out to give mixtures of C11- and C13-adducts. In both reactions, the methano-bridge controls the nucleophilic attacks to the C13 to favor exo selectivity. The photoinduced autorecycling oxidation reactions of 10(+).BF(4)(-) toward some amines under aerobic conditions were carried out to give the corresponding imines (isolated by converting to the corresponding 2,4-dinitrophenylhydrazones) in 719-3286% yield (recycling number of 10(+).BF(4)(-): 7.2-32.9).     

Probing the ruthenium-cumulene bonding interaction: synthesis and spectroscopic studies of vinylidene- and allenylidene-ruthenium complexes supported by tetradentate macrocyclic tertiary amine and comparisons with diphosphine analogues of ruthenium and osmium

The synthesis and spectroscopic properties of trans-[Cl(16-TMC)Ru[double bond]C[double bond]CHR]PF(6) (16-TMC = 1,5,9,13-tetramethyl-1,5,9,13-tetraazacyclohexadecane, R = C(6)H(4)X-4, X = H (1), Cl (2), Me (3), OMe (4); R = CHPh(2) (5)), trans-[Cl(16-TMC)Ru[double bond]C[double bond]C[double bond]C(C(6)H(4)X-4)(2)]PF(6) (X = H (6), Cl (7), Me (8), OMe (9)), and trans-[Cl(dppm)(2)M[double bond]C[double bond]C[double bond]C(C(6)H(4)X-4)(2)]PF(6) (M = Ru, X = H (10), Cl (11), Me (12); M = Os, X = H (13), Cl (14), Me (15)) are described. The crystal structures of 1, 5, 6, and 8 show that the Ru-C(alpha) and C(alpha)-C(beta) distances of the allenylidene complexes fall between those of the vinylidene and acetylide relatives. Two reversible redox couples are observed by cyclic voltammetry for 6-9, with E(1/2) values ranging from -1.19 to -1.42 and 0.49 to 0.70 V vs Cp(2)Fe(+/0), and they are both 0.2-0.3 and 0.1-0.2 V more reducing than those for 10-12 and 13-15, respectively. The UV-vis spectra of the vinylidene complexes 1-4 are dominated by intense high-energy bands at lambda(max) < or = 310 nm (epsilon(max) > or = 10(4) dm(3) mol(-1) cm(-1)), while weak absorptions at lambda(max) > or = 400 nm (epsilon(max) < or = 10(2) dm(3) mol(-1) cm(-1)) are tentatively assigned to d-d transitions. The resonance Raman spectrum of 5 contains a nominal nu(C[double bond]C) stretch mode of the vinylidene ligand at 1629 cm(-1). The electronic absorption spectra of the allenylidene complexes 6-9 exhibit an intense absorption at lambda(max) = 479-513 nm (epsilon(max) = (2-3) x 10(4) dm(3) mol(-1) cm(-1)). Similar electronic absorption bands have been found for 10-12, but the lowest energy dipole-allowed transition is blue-shifted by 1530-1830 cm(-1) for the Os analogues 13-15. Ab initio calculations have been performed on the ground state of trans-[Cl(NH(3))(4)Ru[double bond]C[double bond]C[double bond]CPh(2)](+) at the MP2 level, and imply that the HOMO is not localized purely on the metal center or allenylidene ligand. The absorption band of 6 at lambda(max) = 479 nm has been probed by resonance Raman spectroscopy. Simulations of the absorption band and the resonance Raman intensities show that the nominal nu(C[double bond]C[double bond]C) stretch mode accounts for ca. 50% of the total vibrational reorganization energy, indicating that this absorption band is strongly coupled to the allenylidene moiety. The excited-state reorganization of the allenylidene ligand is accompanied by rearrangement of the Ru[double bond]C and Ru[bond]N (of 16-TMC) fragments, which supports the existence of bonding interaction between the metal and C[double bond]C[double bond]C unit in the electronic excited state.     

Competitive ArC-H and ArC-X (X = Cl, Br) activation in halobenzenes at cationic titanium centers

The titanium methyl cation [Cp*((tBu3P=N)TiCH3]+ [B(C6F5)4]- reacts rapidly with H2 to give the analogous cationic hydride [Cp*((tBu3P=N)TiH(THF)n]+ [B(C6F5)4]- (n = 0, 1), which can be trapped and isolated as its THF adduct 1 x THF (n = 1). When generated in the presence of chloro or bromobenzene, 1 undergoes C-X activation or ortho-C-H activation, depending on the amount of dihydrogen present in the reaction medium. At approximately 4 atm of H2, C-X activation is preferred, giving the halocations [Cp*((tBu3P= N)TiX]+ [B(C6F5)4]- (2X) and C6H6/biphenyl mixtures. At lower pressures of H2 (>1 atm), the beta-halophenyl cations [Cp*((tBu3P=N)Ti(2-X-C6H4)]+ [B(C6F5)4]- (3X) are the products isolated. In the absence of H2, these compounds are quite thermally stable, but undergo beta-halogen elimination upon moderate heating, to give 2X (approximately 20%) and compounds 4X which are the result of reaction between 2X and benzyne via addition of the benzyne C-C triple bond across the Ti-N bond of the phosphinimide ligand. Thus, three separate bond activation processes are operative in this system: direct C-X activation, ortho-C-H activation, and indirect C-X activation via beta-halogen elimination. Mechanistic studies on all three processes have been done and support a radical pathway for direct C-X cleavage, sigma-bond metathesis of the ortho-C-H bond of eta(1)-coordinated C6H5X, and beta-halogen elimination from base-free compound 3X.     

Effect of the N-terminal basic residue on facile Cα-C bond cleavages of aromatic-containing peptide radical cations

Fragmentation of radical cationic peptides [R(G)(n-2)X(G)(7-n)]˙(+) and [R(G)(m-2)XG]˙(+) (X = Phe or Tyr; m = 2-5; n = 2-7) leads selectively to a(n)(+) product ions through in situ C(α)-C peptide backbone cleavage at the aromatic amino acid residues. In contrast, substituting the arginine residue with a less-basic lysine residue, forming [K(G)(n-2)X(G)(7-n)]˙(+) (X = Phe or Tyr; n = 2-7) analogs, generates abundant b-y product ions; no site-selective C(α)-C peptide bond cleavage was observed. Studying the prototypical radical cationic tripeptides [RFG]˙(+) and [KFG]˙(+) using low-energy collision-induced dissociation and density functional theory, we have examined the influence of the basicity of the N-terminal amino acid residue on the competition between the isomerization and dissociation channels, particularly the selective C(α)-C bond cleavage viaβ-hydrogen atom migration. The dissociation barriers for the formation of a(2)(+) ions from [RFG]˙(+) and [KFG]˙(+)via their β-radical isomers are comparable (33.1 and 35.0 kcal mol(-1), respectively); the dissociation barrier for the charge-induced formation of the [b(2)- H]˙(+) radical cation from [RFG]˙(+)via its α-radical isomer (39.8 kcal mol(-1)) was considerably higher than that from [KFG]˙(+) (27.2 kcal mol(-1)). Thus, the basic arginine residue sequesters the mobile proton to promote the charge-remote selective C(α)-C bond cleavage by energetically hindering the competing charge-induced pathways.     

Synthesis, crystal structure and optoelectronic properties of a new unsymmetrical photochromic diarylethene

A new unsymmetrical photochromic diarylethene, 1-(2-methyl-5-phenyl-3-thienyl)-2-[2-methyl-5-(3-trifluoromethylphenyl)-3-thienyl]perfluorocyclopentene (1a), was synthesized and its structure was determined by single-crystal X-ray diffraction analysis. Its optical and electrochemical properties, including photochromic reactivity both in solution and in the solid state (PMMA film and the single-crystalline phase), fluorescence and electrochemical properties were investigated in detail. The compound showed excellent photochromism even in the single-crystalline phase by photo-irradiation. In acetonitrile, the open-ring isomer of diarylethene 1 exhibited relatively strong fluorescence at 470nm when excited at 300nm, and its emission intensity decreased along with the photochromism upon irradiation with 313nm light. Its closed-ring isomer showed almost no fluorescence. The electrochemical properties of diarylethene were investigated by performing cyclic voltammetry experiment and its HOMO and LUMO energy level were calculated.     

Binding studies of DNA with Co(III) coordination compound

The binding of Co(bpy)₂dppz³⁺ to calf thymus DNA was investigated by using absorption and emission spectroscopy, DNA melting techniques, cyclic voltammetry, viscosity and electro phoresis measurements, where bpy is 2,2′-bipyridyl, dppz is dipyrido[3,2-a:2′,3′-c] phenazine. The binding compound shm absorption hypochromicity, fluorescence enhancement, and increasing of DNA melting temperature and the specific viscosity. CV measurement shows the shifts in oxidation-reduction potential and change in peak current with addition of DNA. The compound ie also shown to be more efficient photosensitisers for strand breaks in plasmid DNA.     

The role of chalcogen-chalcogen interactions in the intrinsic basicity acidity of beta-chalcogenovinyl(thio)aldehydes HC([double bond]X)[bond]CH[double bond]CH[bond]CYH

The intrinsic acidity and basicity of a series of beta-chalcogenovinyl(thio)aldehydes HC([double bond]X)[bond]CH[double bond]CH[bond]CYH (X=O, S; Y=Se, Te) were investigated by B3LYP/6-311+G(3df,2p) density functional and G2(MP2) calculations on geometries optimized at the B3LYP/6-31G(d) level for neutral molecules and at the B3LYP/6-31+G(d) level for anions. The results showed that selenovinylaldehyde and selenovinylthioaldehyde should behave as Se bases in the gas phase, because the most stable neutral conformer is stabilized by an X[bond]H...Se (X=O, S) intramolecular hydrogen bond (IHB). In contrast the Te-containing analogues behave as oxygen or sulfur bases, because the most stable conformer is stabilized by typical X...Y[bond]H chalcogen-chalcogen interactions. These compounds have a lower basicity than expected because either chalcogen-chalcogen interactions or IHBs become weaker upon protonation. Similarly, they are also weaker acids than expected because deprotonation results in a significantly destabilized anion. Loss of the proton from the X[bond]H or Y[bond]H groups is a much more favorable than from the C[bond]H groups. Therefore, for Se compounds the deprotonation process results in loss of the X[bond]H...Se (X=O, S) IHBs present in the most stable neutral conformer, while for Te-containing compounds the stabilizing X...Y[bond]H chalcogen-chalcogen interaction present in the most stable neutral conformer becomes repulsive in the corresponding anion.     

Syntheses, reactivity and DFT studies of group 2 and group 12 metal complexes of tris(pyrazolyl)methanides featuring "free" pyramidal carbanions

Reactions of HC(Me2pz)3 with Grignard reagents, dialkyl magnesium compounds and dimethylzinc are reported, together with a DFT study on some of the aspects of this chemistry. Reactions of HC(Me2pz)3 with MeMgX (X=Cl or Br) gave the half-sandwich zwitterionic compounds [Mg((Me)Tpmd)X] (X=Cl (2) or Br (3); (Me)Tpmd(-)=[C(Me2pz)3](-)). Addition of HCl to 2 gave the structurally characterised half-sandwich compound [Mg{HC(Me2pz)3}Cl2(thf)] (4). The zwitterionic sandwich compound [Mg(MeTpmd)2] (5) formed in low yields in the reaction of MeMgX with HC(Me2pz)3 but was readily prepared from HC(Me2pz)3 and either MgnBu2 or MgPh2. The structurally characterised compound 5 contains two "naked" sp3-hybridised carbanions fully separated from the dicationic metal centre. Only by using MgPh2 as starting material could the half-sandwich compound [Mg(MeTpmd)Ph(thf)] (6) be isolated. The zwitterionic sandwich compound 5 reacted with HOTf (OTf(-)=[O3SCF3](-)) to form the dication [Mg{HC(Me2pz)3}2]2+ (7(2+)), which was structurally characterised. Pulsed field gradient spin-echo (PGSE) diffusion NMR spectroscopy revealed both compounds to be intact in solution. In contrast to the magnesium counterparts, HC(Me2pz)3 reacted only slowly with ZnMe2 (and not at all with ZnPh2) to form the half-sandwich zwitterion [Zn(MeTpmd)Me] (8), which contains a cationic methylzinc moiety separated from a single sp3-hybridised carbanion. Density functional calculations on the zwitterions [M(MeTpmd)Me] and [M(MeTpmd)2] (M=Mg, Zn) revealed that the HOMO in each case is a (Me)Tpmd-based carbanion lone pair. The kappa 1C isomers of [M(MeTpmd)Me] were calculated to be considerably less stable than their kappa 3N-bound counterparts, with the largest gain in energy for Mg due to the greater ease of electron transfer from metal to the (Me)Tpmd apical carbon atom on formation of the zwitterion. Moreover, the computed M-C bond dissociation enthalpies of the kappa 1C isomers of [M(MeTpmd)Me] are considerably higher than expected by simple extrapolation from the corresponding computed H-C bond dissociation enthalpy.     

Syntheses,electronic absorption,emission, and ion-binding studies of platinum(III) C empty set N empty set C and terpyridyl complexes containing crown ether pendants

A series of platinum (II) C empty set N empty set C complexes, [Pt(C empty set N empty set C) (L)] (HC empty set N empty set CH=2,6-diphenylpyridine (dppy); L=Ph(2)PB15C5 (1, B15C5=benzo[15]crown-5), Ph(2)PDMP (2, DMP=3,4-dimethoxyphenyl), pyCOA15C5 (3, A15C5=aza[15]crown-5), pyCON(CH(2)CH(2)OCH(3))(2) (4), pyC[triple bond]CB15C5 (5), pyC[triple bond]CDMP (6)) and terpyridyl complexes, [Pt(trpy)(L)](X)(2) (trpy=2,2':6',2'-terpyridine; L=Ph(2)PB15C5, X=OTf (7 a), PF(6) (7 b); X=PF(6), L=Ph(2)PDMP (8), pyC[triple bond]CB15C5 (9), and pyC[triple bond]CDMP (10)) have been successfully synthesized and characterized. The structures of 1, 3, and 7 a have been determined by X-ray crystallography. Excitation of complexes 1-6 in EtOH/MeOH (4:1 v/v) glass gave high-energy structured emission bands, assigned as derived from states of metal-perturbed intraligand (IL) origin. At higher concentrations, complexes 3-6 each displayed an additional, structureless emission band at 600-615 nm, with complexes 5 and 6 showing an obvious increase in the intensity of this emission band when the concentration was increased further. In dichloromethane at room temperature, complexes 3-6 showed, in addition to the high-energy emission at 490-505 nm, an extra, broad emission band at 620-625 nm when the concentration was increased. The emission origins of the low-energy band in glass and in fluid solutions are suggested to be derived from the ground-state oligomerization or aggregation process of the complexes. In the solid state at room temperature, complexes 1-6 each showed a broad, unstructured emission band at 560-600 nm, which was shifted to lower energy upon cooling to 77 K. On the other hand, the terpyridyl analogues 7-10 displayed intense vibronic-structured intraligand (IL) emissions at 460-472 nm in butyronitrile glass at 77 K. Solid-state samples of 9 and 10 displayed strong phosphorescence upon photoexcitation at 298 K and 77 K, tentatively assigned as derived from states of Pt(d pi)-->pi*(trpy) (3)MLCT origin(MLCT=metal-to-ligand charge transfer). The ion-binding properties of complexes 5 and 9 for Na(+), Ba(2+), and K(+) ions have been studied by UV/Vis spectrophotometric methods, and confirmed by ESI mass spectrometric studies. The ion-binding properties for Na(+) ions have also been probed by (1)H NMR experiments. For the same crown ether-containing ligand and the same metal ions, the neutral cyclometalated complexes gave larger binding constants than the positively charged terpyridyl analogues.     

Mixed unsymmetric oxadiazoline and/or imine platinum(II) complexes

Iminoacylation of acetone oxime Me(2)C[double bond, length as m-dash]NOH upon reaction with trans-[PtCl(2)(NCCH(2)CO(2)Me)(2)] and [2 + 3] cycloaddition of acyclic nitrone (-)O(+)N(Me) = C(H)(C(6)H(4)Me-4) to a nitrile ligand in lead to the formation of mono-imine trans-[PtCl(2)(imine-a)(NCCH(2)CO(2)Me)] [imine-a = NH[double bond, length as m-dash]C(CH(2)CO(2)Me)ON = CMe(2)] and mono-oxadiazoline trans-[PtCl(2)(oxadiazoline-a)(NCCH(2)CO(2)Me)] [oxadiazoline-a = [upper bond 1 start]N[double bond, length as m-dash]C(CH(2)CO(2)Me)ON(Me)C[upper bond 1 end](H)(C(6)H(4)Me-4)] unsymmetric mixed ligand complexes, respectively, as the main products. Reactions of or with acetone oxime , cyclic nitrone (-)O(+)N = CHCH(2)CH(2)C[upper bond 1 end]Me(2) or N,N-diethylhydroxylamine give access, in moderate to good yields, to the unsymmetric mixed ligand oxadiazoline and/or imine complexes trans-[PtCl(2)(oxadiazoline-a)(imine-a)] , trans-[PtCl(2)(oxadiazoline-a)(oxadiazoline-b)] [oxadiazoline-b = [upper bond 1 start]N[double bond, length as m-dash]C(CH(2)CO(2)Me)O[lower bond 1 start]NC[upper bond 1 end](H)CH(2)CH(2)C[lower bond 1 end]Me(2)], trans-[PtCl(2)(imine-a)(imine-b)] [imine-b = NH = C(CH(2)CO(2)Me)ONEt(2)] or trans-[PtCl(2)(imine-a)(oxadiazoline-b)] . The cis mono-imine mixed ligand complex cis-[PtCl(2)(imine-a)(NCCH(2)CO(2)Me)] is the major product from the reaction of cis-[PtCl(2)(NCCH(2)CO(2)Me)(2)] with the oxime , while the di-imine compound cis-[PtCl(2)(imine-a)(2)] is a minor product. Reaction of cis-[PtCl(2)(imine-a)(NCCH(2)CO(2)Me)] with N,N-diethylhydroxylamine or the cyclic nitrone affords, in good yields, the unsymmetric mixed ligand complexes cis-[PtCl(2)(imine-a)(imine-b)] or cis-[PtCl(2)(imine-a)(oxadiazoline-b)] , respectively. All these complexes were characterized by elemental analyses, IR and (1)H, (13)C and (195)Pt NMR spectroscopies, and FAB(+)-MS. The X-ray structural analysis of trans-[PtCl(2){NH=C(CH(2)CO(2)Me)ON=CMe(2)}(NCCH(2)CO(2)Me)] is also reported.     

Singlet diradical complexes of ruthenium and osmium: geometrical and electronic structures and their unexpected changes on oxidation

Reaction of HL, HLa (2-[(2-N-phenylamino)phenylazo]pyridine), HLb (2-[{2-N-(4-methylphenyl)amino}phenylazo]pyridine), or HLc (2-[{2-N-(4-chlorophenyl)amino}phenylazo]pyridine), with KRuO4 or OsO4 and PPh3 under exhaustive deoxygenation (PPh3 --> OPPh3) yields diamagnetic compounds ML2. Crystal structure determination for M(La)2 indicates the radical dianion state, L2(.-), for the ligands as evident from the typical N-N bond length of about 1.33 A for a one-electron reduced azo function. The resulting spin-coupled complexes, MIV(L(2.-))2, can be oxidized in two reversible one-electron steps, as probed by cyclic voltammetry and UV-vis-NIR spectroelectrochemistry. The paramagnetic intermediates, [M(La)2]+, are distinguished by intense NIR absorption, largely metal-centered spin as revealed by EPR, and, in the case of [Os(La)2]I3, by crystallographically determined shortening of the NN bond to about 1.30 A, corresponding to a coordinated unreduced azo function. Thus, oxidation of the complex MIV(L(2.-))2 involves partial reduction of the metal in [MIII(L-)2]+ because intramolecular double electron transfer is offsetting the external charge removal. Density-functional theory calculations were employed to confirm the structural features and to support the spectroscopic assignments.     

Ruthenium(II) complexes containing the pentadentate SNNNS chelating ligand 2,6–diacetylpyridine bis(4–(p-tolyl)thiosemicarbazone). Synthesis,reactivity and electrochemistry

Ruthenium(II) heptacoordinate complexes containing the pentadentate SNNNS chelating ligand 2,6–diacetylpyridine bis(4–(p-tolyl)thiosemicarbazone) (L1H2) have been prepared. The compounds were of the type Ru(L1H2)X2 [X=Cl (1);Br (2); SCN (3)],[Ru(L1H2)- (Y)Cl]Cl [Y=imidazole (4); pyridine-N-oxide (5)] and [Ru(L1H2)(PPh3)X]Y, [X=Cl (6), (7);Br (8); Y=ClO4/ PF6]. The complexes were characterised by i.r., u.v.–vis. and n.m.r. spectroscopy and their electrochemical behaviour was examined by cyclic voltammetry. They exhibit a reversible to quasi-reversible RuII/RuIII couple in MeCN solution at a glassy carbon working electrode using an Ag/AgCl electrode as the reference. This revised version was published online in June 2006 with corrections to the Cover Date.