Oxidation of cis-Diamminediacetato PtII with Hydrogen Peroxide Can Give Rise to Two Isomeric PtIV Products

The oxidation of cis-[Pt(NH₃)₂(OAc)₂] with H₂O₂ yields a mixture of two isomers: ctc-[Pt(NH₃)₂(OH)₂(OAc)₂] and ctc-[Pt(NH₃)₂(OH)(OAc)(OH)(OAc)]. Following modification with 4-phenylbutyric (PhB) anhydride, two isomers were separated and characterized; the symmetric ctc-[Pt(NH₃)₂(PhB)₂(OAc)₂] ( 1 ) and the nonsymmetric ctc-[Pt(NH₃)₂(PhB)(OAc)(PhB)(OAc)] ( 2 ). They differ in their log P values and despite having similar cellular uptake and similar DNA platination levels, the symmetric ctc-[Pt(NH₃)₂(OH)₂(OAc)₂] is more than 4-fold more potent than the nonsymmetric isomer in a panel of 4 cancer cell lines.     

Synthesis and Reactivity of Iridium(I) Fluorido Complexes: Oxidative Addition of SF4 at trans-[Ir(F)(CO)(PEt3)2]

The facile access to the Vaska type fluorido complexes trans-[Ir(F)(CO)(PR₃)₂] [ 6 : R = Et, 7 : R = Ph, 8 : R = iPr, 9 : R = Cy, 10 : R = tBu] was achieved by halide exchange at trans-[Ir(Cl)(CO)(PR₃)₂] ( 1 – 5 ) with Me₄NF. Furthermore, the reaction of complex 6 with SF₄ gave cis,trans-[Ir(F)₂(SF₃)(CO)(PEt₃)₂] ( 11 ), whereas 8 – 10 did not react. Reactivity studies revealed that 11 can selectively be manipulated at the sulfur atom by hydrolysis or fluoride abstraction to give cis,trans-[Ir(F)₂(SOF)(CO)(PEt₃)₂] ( 12 ) and cis,trans-[Ir(F)₂(SF₂)(CO)(PEt₃)₂][AsF₆] ( 13 ), respectively.     

Preparation and Properties of Molybdenum and Tungsten Dinitrogen Complexes. 30.1 Syntheses of Zero-Valent Molybdenum Complexes with the DMF Ligand: The Crystal Structure of Trans-[Mo(CO)(DMF)(Ph2PCH2CH2PPh2)2]

Abstract

Treatment of trans-[Mo(N₂)₂(dpe)(dpm)] (dpe = Ph₂PCH₂CH₂PPh₂, dpm = Ph₂PCH₂PPh₂) or trans-[Mo(N₂)₂(dpe)(dpp)] (dpp = Ph₂PCH₂CH₂CH₂PPh₂) with excess DMF in benzene at reflux under Ar resulted in the formation of trans-[Mo(CO)(DMF)(dpe)(dpm)] or trans-[Mo(CO)(DMF)(dpe)(dpp)]. X-ray structural analysis of trans-[Mo(CO)(DMF)(dpe)₂] was performed using single crystals isolated as the minor product from the reaction mixture of trans-[Mo(N₂)₂(dpe)(dpp)] and DMF. Crystal data: C₅₆H₅₅O₂NP₄Mo, monoclinic, space group P2₁, a = 11.145(4), b = 23.425(5), c = 10.516(3) Å, β = 117.17(2)° V = 2442.6(13) ų, D _calcd = 1.35 g/cm³ for Z = 2. This disclosed the relatively long C O bond distance of the carbonyl ligand and the significantly short C=O bond length in the DMF ligand. When recrystallized from benzene/hexane under N₂, trans-[Mo(CO)(DMF)(dpe)(dpm)] was converted into trans-[Mo(CO)(N₂)(dpe)(dpm)].     

Studies on DNA binding behavior of biologically active Cu(II) complexes of Schiff bases containing acyl pyrazolones and 2-ethanolamine

Pyrazolone derivatives (Z)-4-((2-hydroxyethylimino)(p-tolyl)methyl)-3-methyl-1-phenyl-1H-pyrazol-5(4H)-one [PMP-EA] (1), (Z)-1-(3-chlorophenyl)-4-((2-hydroxyethylimino)(p-tolyl)methyl)-3-methyl-1H-pyrazol-5(4H)-one [MCPMP-EA] (2), and (Z)-4-((2-hydroxyethylimino)(p-tolyl)methyl)-3-methyl-1-p-tolyl-1H-pyrazol-5(4H)-one [PTPMP-EA] (3) have been synthesized and characterized. The molecular geometry of 2 has been determined by single-crystal X-ray study. These ligands exist in amine-one tautomeric form in the solid state. Three copper(II) complexes, [Cu(PMP-EA)(H₂O)₂] (4), [Cu(MCPMP-EA)(H₂O)₂] (5), and [Cu(PTPMP-EA)(H₂O)₂] (6), respectively, have been synthesized using these ligands and characterized by microanalytical data, molar conductivity, IR, UV–Visible, FAB-Mass, magnetic measurement, TG-DTA studies, and ESR spectral studies; Cu(II) is five-coordinated with [ML(H₂O)₂] composition. The interaction of the complexes with CT-DNA (calfthymus) was investigated using different methods. The results suggest that the copper complexes bind to DNA via intercalation and can quench the fluorescence intensity of EB bound to DNA.     

Synthesis and structural characterization of cationic octahedral oxorhenium(V) complexes with bidentate imidazole derivatives

Cationic distorted octahedral complexes [ReOCl(OEt)(L)(PPh₃)]X {L = 2-(1-ethylaminomethyl)-1-methylimidazole (eami), 2-(1-methylaminomethyl)-1-methylimidazole (mami), 2-(1-ethylthiomethyl)-1-methylimidazole (etmi); X=ReO₄, PF₆} were prepared by reaction of trans-[ReOCl₃(PPh₃)₂] with a twofold molar excess of L in ethanol under anaerobic conditions. X-ray structure determinations of [ReOCl(OEt)(eami)(PPh₃)](ReO₄) (1a) and its etmi equivalent (3a) were performed. In 1a coordination of the chloride occurs trans to the imidazole nitrogen. However, in 3a the chloride is coordinated trans to the ethereal sulfur donor of etmi.     

Rhenium(V) Complexes with Bidentate N,O-Donor Imidazole Derivatives

The reaction of a two-fold molar excess of the potential N,O-donor ligand 2-(hydroxymethyl)-1-methylimidazole (Hmi) with trans-[ReOCl₃(PPh₃)₂] led to the isolation of cis-[ReOCl₂(mi)(PPh₃)]. An X-ray structure determination indicated that the complex has distorted octahedral geometry, and that mi coordinates as a bidentate with the alcoholate oxygen trans to the oxo group. A similar reaction with 2-(1-ethyloxomethyl)-1-methylimidazole (eomi), the ethyl substituted analogue of Hmi, led to the formation of the oxo-bridged dinuclear complex [(μ-O){ReOCl₂(eomi)₂}₂]. The ligand eomi coordinates as a monodentate via the imidazole nitrogen, with the "hard" ether oxygen uncoordinated. An X-ray crystal structure indicates that the chlorides are trans to each other in the ReN₂Cl₂ planes, which are orthogonal to the O=Re-O-Re=O backbone.     

Chemistry of a family of semiquinone monochelates of carbonyl ruthenium(II) generated by reacting quinones with hydridic species

The reactions of [Ru(H)(Cl)(CO)(PPh₃)₃] with 3,5-di-tert-butyl-o-benzoquinone (dbq) and 3,4,5,6-tetrachloro-o-benzoquinone (tcq) have afforded the corresponding semiquinone complexes [Ru^II(dbsq)(Cl)(CO)(PPh₃)₂] and [Ru^II(tcsq)(Cl)(CO)(PPh₃)₂], respectively. The reaction of [Ru(H)₂(CO)(PPh₃)₃] with tcq has furnished [Ru^II(tcsq)(H)(CO)(PPh₃)₂]. Structure determination of [Ru(dbsq)(Cl)(CO)(PPh₃)₂] has revealed that it is a model semiquinonoid chelate with two equal C---O lengths ( 1.291(6) and 1.296(6) Å). The complexes are one-electron paramagnetic (1.85μ_B) and their EPR spectra in fluid media display a triplet structure (g2.00) due to superhyperfine coupling with two trans-³¹P atoms (A_iso17 G). The stretching frequency of the CO ligand increases by 20 cm⁻¹ in going from [Ru(dbsq)(Cl)(CO)(PPh₃)₂] to [Ru(tcsq)(Cl)(CO)(PPh₃)₂] consistent with electron withdrawal by chloro substituents. For the same reason the E_1/2 values of the cyclic voltammetric quinone/semiquinone and semiquinone/catechol couples undergo a shift of 500 mV to higher potentials between [Ru(dbsq)(Cl)(CO)(PPh₃)₂] and [Ru(tcsq)(Cl)(CO)(PPh₃)₂].     

Synthesis,characterization and X-ray crystal structures of <Emphasis Type="Italic">N</Emphasis>-2-pyridinyl carbonyl-2-pyridine carboximidate copper(II) complexes

Two copper complexes, [Cu(bpca)(4,4′-bpyH)(H₂O)(ClO₄)]ClO₄·H₂O (1) and [Cu₄(bpca)₄(mpba)]·3H₂O (2) [bpca = N-2-pyridinylcarbonyl-2-pyridine-carboximidate; mpba = 1,3-phenylenebis(oxamate)] were synthesized and characterized by physico-chemical and spectroscopic techniques. Complex 1 crystallizes in the Triclinic P-1 space group while complex 2 is in the Monoclinic space group C2/c. Bpca acts as a tridentate ligand through its three nitrogen atoms in these species. They exhibit 2D supramolecular architectures through hydrogen bonds and short-distance intermolecular interactions. Magnetic measurements in the range 2–300 K have shown weak antiferromagnetic interactions between the adjacent copper ions in complex 2. Electronic supplementary material  The online version of this article (doi:) contains supplementary material, which is available to authorized users.     

Syntheses of Molybdenum and Tungsten Imido Alkylidene Complexes that Contain a Bidentate Oxo/Thiolato Ligand

3,3′,5,5′-Tetra-tert-butyl-2′-sulfanyl[1,1′-biphenyl]-2-ol (H₂[^tBu₄OS]) was prepared in 24 % yield overall from the analogous biphenol using standard techniques. Addition of H₂[^tBu₄OS] to Mo(NAr)(CHCMe₂Ph)(2,5-dimethylpyrrolide)₂ led to formation of Mo(NAr)(CHCMe₂Ph)[^tBu₄OS], which was trapped with PMe₃ to give Mo(NAr)(CHCMe₂Ph)[^tBu₄OS](PMe₃) ( 1 (PMe₃)). An X-ray crystallographic study of 1 (PMe₃) revealed that two structurally distinct square pyramidal molecules are present in which the alkylidene ligand occupies the apical position in each. Both 1 (PMe₃)_A and 1 (PMe₃)_B are disordered. Mo(NAd)(CHCMe₂Ph)(^tBu₄OS)(PMe₃) ( 2 (PMe₃); Ad=1-adamantyl) and W(NAr)(CHCMe₂Ph)(^tBu₄OS)(PMe₃) ( 3 (PMe₃)) were prepared using analogous approaches. 1 (PMe₃) reacts with ethylene (1 atm) in benzene within 45 minutes to give an ethylene complex Mo(NAr)(^tBu₄OS)(C₂H₄) ( 4 ) that is isolable and relatively stable toward loss of ethylene below 60 °C. An X-ray study shows that the bond distances and angles for the ethylene ligand in 4 are like those found for bisalkoxide ethylene complexes of the same general type. Complex 1 (PMe₃) in the presence of one equivalent of B(C₆F₅)₃ catalyzes the homocoupling of 1-decene, allyltrimethylsilane, and allylboronic acid pinacol ester at ambient temperature. 1 (PMe₃), 2 (PMe₃), and 3 (PMe₃) all catalyze the ROMP of rac-endo,exo-5,6-dicarbomethoxynorbornene (rac-DCMNBE) in the presence of B(C₆F₅)₃, but the polyDCMNBE that is formed has a random structure.     

Reactivity of [ReOX3(PPh3)2] and [ReOX3(AsPh3)2] towards 2-(2-hydroxyphenyl)-1H-benzimidazole: Synthesis, X-ray studies, spectroscopic characterization and DFT calculations for [ReOX2(hpb)(EPh3)] and [ReO(OMe)(hpb)2]·MeCN

The paper presents a combined experimental and computational study of mono- and disubstituted Re(V) oxocomplexes obtained in the reactions of [ReOX₃(EPh₃)₂] (X = Cl, Br; E = P, As) with 2-(2-hydroxyphenyl)-1H-benzimidazole (Hhpb). From the reactions of [ReOX₃(PPh₃)₂] with Hhpb in molar ratio 1:1 cis and trans stereoisomers of [ReOX₂(hpb)(PPh₃)] were isolated, whereas the [ReOX₃(AsPh₃)₂] oxocompounds react with Hhpb to give only cis-halide isomers. The [ReOX₂(hpb)(EPh₃)] and [ReO(OMe)(hpb)₂]·MeCN complexes have been characterized spectroscopically and structurally (by single-crystal X-ray diffraction). The DFT and TDDFT calculations have been carried out for the trans-[ReOBr₂(hpb)(PPh₃)], cis-[ReOBr₂(hpb)(AsPh₃)] and [ReO(OMe)(hpb)₂], and their UV–Vis spectra have been discussed on this basis.     

Chelating Phosphorus–An O,C, O-Coordinating Pincer-Type Ligand Coordinating PIII and PV Centres

The sequence of reactions of the phosphorus-containing aryllithium compound 5-t-Bu-1,3-[(P(O)(O-i-Pr)₂]₂C₆H₂Li (ArLi) with Ph₂PCl, KMnO₄, elemental sulfur and elemental selenium, respectively, gave the aryldiphenylphosphane chalcogenides 5-t-Bu-1,3-[(P(O)(O-i-Pr)₂]₂C₆H₂P(E)Ph₂ ( 1 , E=O; 2 , E=S; 3 , E=Se). Compound 1 partially hydrolysed giving [5-t-Bu-1-{(P(O)(O-i-Pr)₂}-3-{(P(O)(OH)₂}C₆H₂]P(O)Ph₂ ( 4 ). The reaction of ArLi with PhPCl₂ provided the benzoxaphosphaphosphole [1(P), 3(P)-P(O)(O-i-Pr)OPPh-6-t-Bu-4-P(O)(O-i-Pr)₂]C₆H₂P ( 5i ) as a mixture of the two diastereomers. The oxidation of 5i with elemental sulfur gave the benzoxaphosphaphosphole sulfide [1(P), 3(P)-P(O)(O-i-Pr)OP(S)Ph-6-t-Bu-4-P(O)(O-i-Pr)₂]C₆H₂ ( 5 ) as pair of enantiomers P1(R), P3(S)/P1(S), P3(R) of the diastereomer (RS/SR)- 5 ( 5b ). The aryldiphenylphosphane 5-t-Bu-1,3-[(P(O)(O-i-Pr)₂]₂C₆H₂PPh₂ ( 6 ) was obtained from the reaction of the corresponding aryldiphenylphosphane sulfide 2 with either sodium hydride, NaH, or disodium iron tetracarbonyl, Na₂Fe(CO)₄. The oxidation of the aryldiphenylphosphane 6 with elemental iodine and subsequent hydrolysis yielded the aryldiphenyldioxaphosphorane 9-t-Bu-2,6-(OH)-4,4-Ph₂-3,5-O₂-2,6-P₂-4λ⁵-P-[5.3.1.0]-undeca-1(10),7(11),8-triene ( 7 ). Both of its diastereomers, (RR/SS)- 7 ( 7a ) and (RS/SR)- 7 ( 7b ), were separated as their chloroform and i-propanol solvates, 7a ⋅2CHCl₃ and 7b ⋅i-PrOH, respectively. DFT calculations accompanied the experimental work.     

Peptide models XVI. The identification of selected HCO—L—SER—NH2 conformers via a systematic grid search using ab initio potential energy surfaces

Multidimensional conformational analysis (MDCA) predicted the existence of nine stable backbone conformations (α_L, α_D, β_L, γ_L, γ_D, δ_L, δ_D, ϵ_L, and ϵ_D) on the 2D-Ramachandran map, E = E(ϕ, ψ), for a single amino acid diamide (HCONH-CHR-CONH₂). The potential energy hypersurfaces (E = E[ϕ, ψ, χ₁, χ₂]) of For-L-Ser-NH₂ associated with the α_L-, bgr;_L-, γ_L-, δ_L-, and ϵ_L-type stable backbone orientations are investigated in this article. An appropriate number of side-chain rotamers is associated with each of the backbone conformers. In the case of serine, where R = −CH₂OH, the two sidechain torsional angles (χ₁, χ₂) should lead to 3 * 3 = 9 different sidechain orientations according to MDCA. For certain backbone structures, some of the sidechain conformations were nonexistent. © 1996 by John Wiley & Sons, Inc.     

Synthesis,crystal structures and properties of two Cd(II) complexes based on Zaltoprofen

Abstract

Two metal-organic coordination complexes, [Cd(Zaltoprofen)(phen)]_n (1) and [Cd(Zaltoprofen)(btz)]_n (2) (where Zaltoprofen = 5-(1-carboxyethyl)-2-(phenylthio)phenylacetic acid, phen = 1,10-phenanthroline, btz = thiabendazole), have been synthesized by reaction of Cd(NO₃)₂ with Zaltoprofen, 1,10-phenanthroline or thiabendazole under hydrothermal conditions and characterized by single crystal X-ray diffraction, IR spectra, elemental analyses, powder X-ray diffraction (XRD), electronic spectra (UV-vis) and fluorescent properties. Compound 1 crystallizes in the monoclinic P21/c space group and 2 in the monoclinic system with space group P21/n. [Cd(Zaltoprofen)(phen)]_n (1) features a 1-D zigzag chain. The zigzag chains are linked to form a 2-D layer through π–π stacking interactions. [Cd(Zaltoprofen)(btz)]_n (2) displays a 2D net with alternately arranged left- and right-handed helical chains.     

Cobalt and nickel coordination polymers containing 3-pyridylnicotinamide and five-membered ring dicarboxylates

Cobalt and nickel coordination polymers containing the conformationally flexible 3-pyridylnicotinamide (3-pna) ligand and a five-membered ring-based dicarboxylate ligand have been prepared and structurally characterized via single-crystal X-ray diffraction. [Co(tpdc)(3-pna)]_n (1) was prepared using 2,5-thiophenedicarboxylic acid (H₂tpdc). This material shows a 2-D layer structure containing {Co₂(OCO)₂} dimers linked by tpdc and 3-pna ligands. Compound 1 manifests an underlying 3,5-connected (4²6)(4²6⁷8) 3,5L2 topology. The isostructural pair of solids [Co(D-cam)(3-pna)(H₂O)₂]_n (2) and [Ni(D-cam)(3-pna)(H₂O)₂]_n (3) was obtained from the chiral D-camphorate (D-cam) ligand. These two materials possess acentric ribbon coordination polymer motifs. Compound 1 manifests antiferromagnetic coupling concomitant with Kramers doublet formation. Thermal properties of these materials are also discussed.     

Regioselective homogeneous hydrogenation of heteroaromatic nitrogen compounds by use of [RuH(CO)(NCMe)2(PPh3)2]BF4 as the precatalyst

Summary The complex [RuH(CO)(NCMe)₂(PPh₃)₂]BF₄ (1) is an efficient and regioselective catalyst precursor for the hydrogenation of polyaromatic nitrogen compounds such as quinoline (Q), isoquinoline (iQ), indole (ln), 5,6- and 7,8-benzoquinoline (BQ) and acridine (A) under relatively mild reaction conditions (125 °C, 4 atm H₂). The order of individual initial rates was: A > Q > 5,6-BQ > 7,8-BQ > ln > iQ, reflecting both steric and electronic effects. For the regioselective homogeneous hydrogenation of A to 9,10-dihydroacridine (DHA) catalysed by complex (1), a kinetic study was carried out; the experimentally determined rate law was r = k ₁ [Ru] [H₂]. These findings are consistent with a mechanism involving the hydrogenation of [RuH(CO)(A)(NCMe)(PPh₃)₂]BF₄ to yield DHA and the unsaturated species [RuH(CO)(NCMe)(PPh₃)₂]BF₄ in the rate-determining step.     

Synthesis,Crystal Structures,and Optical Properties of AM2(OH)(SeO3)2 (A = Na,Rb; M = Mg,Zn)

Sodium magnesium selenite NaMg₂(OH)(SeO₃)₂ and rubidium zinc selenite RbZn₂(OH)(SeO₃)₂ were prepared by hydrothermal reactions. The crystal structures of the title compounds were determined by single‐crystal X‐ray diffraction. NaMg₂(OH)(SeO₃)₂ crystallizes in the orthorhombic space group Pnma (no. 62) with lattice parameters a = 13.1919(10), b = 6.0415(4), c = 8.2182(6) Å, and Z = 4 and RbZn₂(OH)(SeO₃)₂ crystallizes in the triclinic space group P$\bar{1}$ (no. 2) with lattice parameters a = 4.8698(5), b = 7.3446(8), c = 11.7796(12) Å, α = 82.554(3), β = 78.456(2), γ = 71.603(3)°,and Z = 2. The structure of NaMg₂(OH)(SeO₃)₂ is a three‐dimensional framework consisting of edge‐sharing MgO₆ octahedra and trigonal pyramidal SeO₃^2– groups, whereas the structure of RbZn₂(OH)(SeO₃)₂ is a two‐dimensional layers structure consisting of corner‐sharing [Zn₂O₇] dimers linked by trigonal pyramidal SeO₃^2– groups. The compounds were characterized by the solid state UV/Vis/NIR diffuse reflectance, and FT‐IR spectroscopy.     

Metal catalysed Brooke rearrangement of 3-Halo-1-(trimethylsilyl) propan-2-one (Halo = Cl or Br)

The complexes [IrH(CO)(PPh₃)₃], trans-[IrCI(CO)- (PPh₃)₂], [RhH(PPh₃)₄], [Pd(PPh₃)₄], [Pt(trans-stilbene)(PPh₃)₂] and [Pt(η³-CH₂-COCH₂)-(PPh₃)₂] catalyse the rearrangement of Me₃SiCH₂C(O)CH₂Cl to CH₂?C(OSiMe₃)-CH₂Cl.     

Nitric oxide and singlet oxygen photo-generation by light irradiation in the phototherapeutic window of a nitrosyl ruthenium conjugated with a phthalocyanine rare earth complex

The photochemical, photophysical and photobiological studies of a mixture containing cis-[Ru(H-dcbpy⁻)₂(Cl)(NO)] (H₂-dcbpy = 4,4′-dicarboxy-2,2′-bipyridine) and Na₄[Tb(TsPc)(acac)] (TsPc = tetrasulfonated phthalocyanines; acac = acetylacetone), a system capable of improving photodynamic therapy (PDT), were accomplished. cis-[Ru(H-dcbpy⁻)₂(Cl)(NO)] was obtained from cis-[Ru(H₂-dcbpy)₂Cl₂]·2H₂O, whereas Na₄[Tb(TsPc)(acac)] was obtained by reacting phthalocyanine with terbium acetylacetonate. The UV–Vis spectrum of cis-[Ru(H-dcbpy⁻)₂(Cl)(NO)] displays a band in the region of 305 nm (λ_max in 0.1 mol L⁻¹ HCl)(π–π*) and a shoulder at 323 nm (MLCT), while the UV–Vis spectrum of Na₄[Tb(TsPc)(acac)] presents the typical phthalocyanine bands at 342 nm (Soret λ_max in H₂O) and 642, 682 (Q bands). The cis-[Ru(H-dcbpy⁻)₂(Cl)(NO)] FTIR spectrum displays a band at 1932 cm⁻¹ (Ru–NO⁺). The cyclic voltammogram of the cis-[Ru(H-dcbpy⁻)₂(Cl)(NO)] complex in aqueous solution presented peaks at E = 0.10 V (NO^+/0) and E = −0.50 V (NO^0/−) versus Ag/AgCl. The NO concentration and ¹O₂ quantum yield for light irradiation in the λ > 550 nm region were measured as [NO] = 1.21 ± 0.14 μmol L⁻¹ and ø_OS = 0.41, respectively. The amount of released NO seems to be dependent on oxygen concentration, once the NO concentration measured in aerated condition was 1.51 ± 0.11 μmol L⁻¹ The photochemical pathway of the cis-[Ru(H-dcbpy⁻)₂(Cl)(NO)]/Na₄[Tb(TsPc)(acac)] mixture could be attributed to a photoinduced electron transfer process. The cytotoxic assays of cis-[Ru(H-dcbpy^-)₂(Cl)(NO)] and of the mixture carried out with B16F10 cells show a decrease in cell viability to 80% in the dark and to 20% under light irradiation. Our results document that the simultaneous production of NO and ¹O₂ could improve PDT and be useful in cancer treatment.     

Ruthenium(II) carbonyl complexes with N-[di(alkyl/aryl)carbamothioyl]benzamide derivatives and triphenylphosphine as effective catalysts for oxidation of alcohols

Ruthenium(II) complexes, [RuCl(L)(CO)(PPh₃)₂] {where L?=?N-[di(alkyl/aryl)carbamothioyl]benzamide derivatives}, are prepared from reaction between [RuHCl(CO)(PPh₃)₃] and N-[di(alkyl/aryl)carbamothioyl]benzamide derivatives in toluene and characterized by elemental analysis and spectral data (electronic, infrared, ¹H NMR, and ³¹P NMR). The combination of [RuCl(L)(CO)(PPh₃)₂] (0.01?mmol) and N-methylmorpholine-N-oxide (NMO) (3?mmol) is an active catalyst for the oxidation of primary, secondary, cyclic, allylic, aliphatic, and benzylic alcohols to their corresponding aldehydes and ketones at room temperature. The oxidation protocol is simple to operate and gives the corresponding carbonyl compounds good to excellent yields.     

Reactivity of carbyne and carbene complexes of molybdenum and tungsten

Summary The interconversion of carbyne, carbyne and hydride complexes derived from protonations oftrans-[M(CNMe)₂(dppe)₂](M = Mo or W) has been studied. The initial site of protonation is shown to be the isonitrile nitrogen and all protonations proceed through the common carbyne intermediatetrans-[M(CNHMe)(CNMe)(dppe)2]⁺. The CNHMe group in traps-[M(CNHMe)₂(dppe)₂]²⁺ is shown to be susceptible to electrophilic attack at N and nucleophilic attack at ligating C, the new complexestrans-[W(CNH2Me)(CNHMe)(dppe)₂](BF₄)₃ andtrans-[Mo(CHNHMe)(CNHMe)(dppe)2]BF4 being formed, respectively.