New mesomorphic organocyclosiloxanes I. Thermal behaviour and mesophase structure of organocyclotetrasiloxanes

cis-Cyclotetrasiloxanes of the formula cis-[PhSi(O)(OSiMe₂ R)]₄ with R = Me, CH₂Cl, CH CH₂ and cis-[ClC₆H₄Si(O)(OSiMe₃)]₄ were synthesized and investigated in terms of their thermotropic phase transitions. Two ordered phases were observed for the cis-cyclotetrasiloxanes, one at lower temperature exhibiting the properties of a crystal and one at higher temperature exhibiting the properties of a plastically crystalline (3D) mesophase. A detailed examination of the mesophase behaviour and mesophase structure of octaphenylcyclotetrasiloxane was also carried out. It was shown that the thermal properties and structural characteristics of the mesophase are influenced by the structural characteristics of the substituent attached at the silicon atom in the tetracyclosiloxane. The new mesomorphic cis-cyclotetrasiloxanes are by far the largest molecules reported to date as forming plastic crystals, and the temperature region of the mesophase is much broader than in other plastic crystals. All five cyclotetrasiloxanes studied were found to be isomorphous in the 3D-mesophase and the low temperature forms of the two cis-cyclotetrasiloxanes: PhSi(O)(OSiMe₂ R)₄ (R = Me, CH CH₂) were also isomorphous.     

Synthesis and mesomorphic properties of cis-penta[(phenyl)(trimethylsiloxy)]cyclopentasiloxane

New stereoregular cis-penta[(phenyl)(trimethylsiloxy)]cyclopentasiloxane cis-[PhSi(O)(OSiMe₃)]₅ was synthesized. According to the data from DSC, X-ray diffraction, and polarization microscopy, the noncrystallizable cyclopentasiloxane exists in the mesomorphic state throughout the temperature range below the temperature of destruction and is transformed into mesomorphic glass below the glass transition temperature. This compound possesses the polymesomorphic properties and forms two mesomorphic modifications. The type of mesomorphic ordering for these modifications was determined. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 7, pp. 1353–1358, July, 2007.     

Synthesis,Structures, and Thermal Properties of Symmetric and Janus “Lantern Cage” Siloxanes

Symmetric and asymmetric (Janus-type) new “lantern cage” siloxanes (PhSiO_1.5)₄(Me₂SiO)₄(RSiO_1.5)₄ (R=Ph or iBu) were synthesized through reaction of all-cis-[PhSi(OSiMe₂Br)O]₄ with all-cis-[RSi(OH)O]₄ (R=Ph or iBu). These precursors were obtained by facile two or three-step reactions from commercially available compounds. The spectroscopic properties of the resulting products were fully characterized and they showed high thermal stability and sublimation without decomposition. The crystal structures clearly indicated that the internal vacancy volumes of the lantern cages are considerably larger than that of octaphenylsilsesquioxane (PhSiO_1.5)₈. DFT calculations of the lantern cage showed a distinctly different electronic state from that of octasilsesquioxane. These results suggest that lantern cage siloxanes have a characteristic “field” in the molecule.     

Unraveling the Mechanism of Water Oxidation Catalyzed by Nonheme Iron Complexes

Density functional theory (DFT) is employed to: 1) propose a viable catalytic cycle consistent with our experimental results for the mechanism of chemically driven (Ce^IV) O₂ generation from water, mediated by nonheme iron complexes; and 2) to unravel the role of the ligand on the nonheme iron catalyst in the water oxidation reaction activity. To this end, the key features of the water oxidation catalytic cycle for the highly active complexes [Fe(OTf)₂(Pytacn)] (Pytacn: 1‐(2′‐pyridylmethyl)‐4,7‐dimethyl‐1,4,7‐triazacyclononane; OTf: CF₃SO₃^?) ( 1 ) and [Fe(OTf)₂(mep)] (mep: N,N′‐bis(2‐pyridylmethyl)‐N,N′‐dimethyl ethane‐1,2‐diamine) ( 2 ) as well as for the catalytically inactive [Fe(OTf)₂(tmc)] (tmc: N,N′,N′′,N′′′‐tetramethylcyclam) ( 3 ) and [Fe(NCCH₃)(^MePy₂CH‐tacn)](OTf)₂ (^MePy₂CH‐tacn: N‐(dipyridin‐2‐yl)methyl)‐N′,N′′‐dimethyl‐1,4,7‐triazacyclononane) ( 4 ) were analyzed. The DFT computed catalytic cycle establishes that the resting state under catalytic conditions is a [Fe^IV(O)(OH₂)(LN₄)]²⁺ species (in which LN₄=Pytacn or mep) and the rate‐determining step is the O?O bond‐formation event. This is nicely supported by the remarkable agreement between the experimental (ΔG^≠=17.6±1.6 kcal mol^?1) and theoretical (ΔG^≠=18.9 kcal mol^?1) activation parameters obtained for complex 1 . The O?O bond formation is performed by an iron(V) intermediate [Fe^V(O)(OH)(LN₄)]²⁺ containing a cis‐Fe^V(O)(OH) unit. Under catalytic conditions (Ce^IV, pH 0.8) the high oxidation state Fe^V is only thermodynamically accessible through a proton‐coupled electron‐transfer (PCET) process from the cis‐[Fe^IV(O)(OH₂)(LN₄)]²⁺ resting state. Formation of the [Fe^V(O)(LN₄)]³⁺ species is thermodynamically inaccessible for complexes 3 and 4 . Our results also show that the cis‐labile coordinative sites in iron complexes have a beneficial key role in the O?O bond‐formation process. This is due to the cis‐OH ligand in the cis‐Fe^V(O)(OH) intermediate that can act as internal base, accepting a proton concomitant to the O?O bond‐formation reaction. Interplay between redox potentials to achieve the high oxidation state (Fe^V?O) and the activation energy barrier for the following O?O bond formation appears to be feasible through manipulation of the coordination environment of the iron site. This control may have a crucial role in the future development of water oxidation catalysts based on iron.     

Synthesis, structure and catalytic activity of the first iridium(I) siloxide versus chloride complexes with 1,3-mesitylimidazolin-2-ylidene ligand

The first iridium(I) complex containing siloxyl and N-heterocyclic carbene ligand such as [Ir(cod)(IMes)(OSiMe₃)] (1) and [Ir(CO)₂(IMes)(OSiMe₃)] (3) have been synthesized and their structures solved by spectroscopy and X-ray methods as well as catalytic properties in selected hydrogenation reactions have been presented in comparison to their chloride analogues, i.e. [Ir(Cl)(cod)(IMes)] (2) and [Ir(Cl)(CO)₂(IMes)] (4). The attempts at synthesis of iridium(I) complex with tert-butoxyl ligand has failed as leading instead to the iridium hydroxide complex [Ir(cod)(OH)(IMes)] (5) whose X-ray structure has also been solved. All complexes (1)-(5) show square planar geometry typical of the four-coordinated iridium complexes. Catalytic activity of complexes 1 and 2 was tested in transfer hydrogenation of acetophenone and hydrogenation of olefins.     

Mononuclear Polypyridylruthenium(II) Complexes with High Membrane Permeability in Gram‐Negative Bacteria—in particular Pseudomonas aeruginosa

Ruthenium(II) complexes containing the tetradentate ligand bis[4(4′‐methyl‐2,2′‐bipyridyl)]‐1,n‐alkane (“bb_n”; n=10 and 12) have been synthesised and their geometric isomers separated. All [Ru(phen)(bb_n)]²⁺ (phen=1,10‐phenanthroline) complexes exhibited excellent activity against Gram‐positive bacteria, but only the cis‐α‐[Ru(phen)(bb₁₂)]²⁺ species showed good activity against Gram‐negative species. In particular, the cis‐α‐[Ru(phen)(bb₁₂)]²⁺ complex was two to four times more active than the cis‐β‐[Ru(phen)(bb₁₂)]²⁺ complex against the Gram‐negative strains. The cis‐α‐ and cis‐β‐[Ru(phen)(bb₁₂)]²⁺ complexes readily accumulated in the bacteria but, significantly, showed the highest level of uptake in Pseudomonas aeruginosa. Furthermore, the accumulation of the cis‐α‐ and cis‐β‐[Ru(phen)(bb₁₂)]²⁺ complexes in P. aeruginosa was considerably greater than in Escherichia coli. The uptake of the cis‐α‐[Ru(phen)(bb₁₂)]²⁺ complex into live P. aeruginosa was confirmed by using fluorescence microscopy. The water/octanol partition coefficients (log P) were determined to gain understanding of the relative cellular uptake. The cis‐α‐ and cis‐β‐[Ru(phen)(bb_n)]²⁺ complexes exhibited relatively strong binding to DNA (K_b≈10⁶ M ^?1), but no significant difference between the geometric isomers was observed.     

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.     

SYNTHESIS AND CRYSTAL STRUCTURE OF OXAMIDATO-BRIDGED BINUCLEAR COPPER(II) COMPLEXES

Abstract

The compounds [Cu(oxpn)] (1), [(bpy)(H₂O)Cu(μ-cis-oxpn)Cu(H₂O)] · 2NO₃ · 2H₂O (2) and [(Him)(NO₃)Cu(μ-trans-oxpn)Cu(Him)(NO₃)] (3), where oxpn is the dianion of N,N′-bis(3-aminopropyl)oxamide, bpy is bipyridine and Him is imidazole, were prepared and characterized by elemental analysis and IR spectra. Complex (2) was also studied by thermochemical analysis and its structure determined by X-ray crystallography. The structure of complex (2) consists of binuclear copper(II) molecules in which the copper(II) atoms are bridged by an oxamidato group in the cis conformation resulting a copper-copper distance of 5.21 Å. Both copper(II) ions are in square-pyramidal surroundings with almost coplanar basal planes and a water molecule occupying the apical positions. The N atoms of the oxamidato moiety are trigonal. Two lattice water molecules together with the two coordinated ones hydrogen bond with nitrate ions.     

Synthesis,structure, and properties of sodium <Emphasis Type="Italic">cis</Emphasis>-tetraethylcyclotetrasiloxanolate and new mesomorphic <Emphasis Type="Italic">cis</Emphasis>-tetra[ethyl(trimethylsiloxy)]cyclotetrasiloxane

Hydrolytic condensation of ethyltriethoxysilane in the presence of NaOH (Si: NaOH = 1) gave crystal solvate of sodium cis-tetraethyltetrasiloxanolate {(Na⁺)₄[EtSi(O)O⁻]₄}·nL (1, L = EtOH, H₂O) in high yield. The molecular structure of compound 1 at L = EtOH, n = 8 was determined by X-ray diffraction analysis. The reaction of compound 1 with trimethylchlorosilane affords cis-tetra[ethyl(trimethylsiloxy)]cyclotetrasiloxane cis-[EtSi(O)OSiMe₃]₄, which is the first representative of the group of mesomorphic cyclotetrasiloxanes containing alkyl groups. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 1, pp. 74–79, January, 2007.     

Synthesis of macrocyclic tris-cis-tris-trans- dodeca[(phenyl)(hydroxy)]cyclododecasiloxane in carbonic acid solution

The possibility to synthesize stereoregular tris-cis-tris-trans- dodeca[(phenyl)(hydroxy)]cyclododecasiloxane (tris-cis-tris-trans-[PhSi(O)OH]12) in an inorganic liquid medium – aqueous carbonic acid solution – was shown. The interaction of polyhedral phenylcoppersodiumsiloxane, {[(C₆H₅Si(O)O^?]₁₂(Cu₂⁺)₄(Na⁺)₄}*(L)_m (L?=?Buⁿ OH, H₂O), with carbonic acid can be considered as a new ‘green’ method to obtain functional organosiloxane macrocycles. In contrast to the known methods, no organic solvents were used during the reaction. The identification of the structure of the end compound was performed by means of NMR and Infrared spectroscopy as well as X-ray crystallography.     

Coordination modes of 2-hydroxynicotinic acid in second- and third-row transition metal complexes

The new Pd(II), Pt(II), Re(V), Mo(VI) and W(VI) complexes of 2-hydroxynicotinic acid (H₂nicO), trans-[PdCl(HnicO)(PPh₃)₂]·0.75CH₃CN (1), K[PdCl(HnicO)₂]·H₂O (2), [Pd(HnicO)₂(bipy)] (3), cis-[PtCl(HnicO)(PPh₃)₂]·0.75CH₃OH·0.5H₂O (4), [PtCl(HnicO)(bipy)] (5), cis-[ReOI₂(HnicO)(PPh₃)] (6), Na₂[Mo₂O₆(HnicO)₂]·5H₂O (7), Na₂[Mo₄O₁₂(HnicO)₂]·2H₂O (8) and Na₂[W₂O₆(HnicO)₂]·5H₂O (9) have been prepared. The crystal structures of 1 and 4, were determined by X-ray diffraction and show the HnicO⁻ ligand coordinated to palladium or platinum through the nitrogen atom only. Infrared, Raman, ¹H and ¹³C{¹H} NMR spectroscopic data for the complexes are presented and are in agreement with the crystallographic results.     

Syntheses and structural characterizations of the octahedral boride clusters [Rh2Ru4H(CO)16−2x (nbd) x B] (x=1,2) and gold(I) phosphine derivatives (nbd=norbornadiene)

The reaction of less than one equivalent of [Rh₂Cl₂(nbd)₂] with [Ru₄H(CO)₁₂BH]⁻, which contains a semi-interstitial boron atom, yields the heterometallic boride clustercis-[Rh₂Ru₄H(CO)₁₂(nbd)₂B] which has been characterized by spectroscopic and X-ray diffraction methods. The cluster has an octahedral core, consistent with an 86 electron count. Deprotonation yields the conjugate basecis-[Rh₂Ru₄(CO)₁₂(nbd)₂B]⁻ which has been isolated and fully characterized as the [(Ph₃P)₂N]⁺ salt. There is little structural perturbation upon going fromcis-[Rh₂Ru₄H(CO)₁₂(nbd)₂B] tocis-[Rh₂Ru₄(CO)₁₂(nbd)₂B]⁻ and neither cluster shows a tendency for the formation of thetrans skeletal isomer in contrast to the analogous carbonyl clustercis-[Rh₂Ru₄(CO)₁₆B]⁻. If the reaction of [Rh₂Cl₂(nbd)₂] with [Ru₄H(CO)₁₂BH]⁻ is allowed to proceed for 30 min and [R ₃PAuCl] (R=Ph, C₆H₁₁, 2-MeC₆H₄) is then added, the clusterscis-[Rh₂Ru₄(CO)₁₂(nbd)₂B(AuPR₃)] andcis-[Rh₂Ru₄(CO)₁₄(nbd)B(AuPR₃)] are formed in yields that are dependent upon the initial reaction period. The single crystal structures ofcis-[Rh₂Ru₄(CO)₁₂(nbd)₂B(AuPPh₃)] andcis-[Rh₂Ru₄(CO)₁₄(nbd)B(AuPPh₃)] are reported. In contrast to their all-carbonyl analoguescis-[Rh₂Ru₄(CO)₁₆B(AuPR ₃)] (R=Ph or C₆H₁₁), the nbd derivatives do not undergocis →trans skeletal isomerism.     

Reactions of cisplatin hydrolytes, cis-[Pt(15NH3)2(H2O) 2]2+, with N-acetyl-L-cysteine

The reaction of cis-[Pt(¹⁵NH₃)2(H₂O) ₂] ²⁺ (3) with N-acetylcysteine [H₃accys] was investigated in aqueous solution. In this reaction, the ammine in the platinum complex formed was liberated. A mono-dentate sulfur-boundplatinum(II) product cis-[Pt(¹⁵NH₃)₂(H₂O)(H2accys-S)]⁺ (7) and six-membered che-late ring complex cis-[Pt(¹⁵NH₃)₂ (Haccys-S,O)] (8) were formed in solution. The dinuclear sulfur-bridged complex 9, giving a broad peak in ¹⁵N NMR, was also observed, but only present in very tiny amounts. The mass spectrometry (ES-MS) was undertaken from this re action, and the product detected was only the dinuclear sulfur bridged platinum species and species related to it by ammine loss.     

Bifunctional Rhenium Complexes for the Catalytic Transfer‐Hydrogenation Reactions of Ketones and Imines

The silyloxycyclopentadienyl hydride complexes [Re(H)(NO)(PR₃)(C₅H₄OSiMe₂tBu)] (R=iPr ( 3 a ), Cy ( 3 b )) were obtained by the reaction of [Re(H)(Br)(NO)(PR₃)₂] (R=iPr, Cy) with Li[C₅H₄OSiMe₂tBu]. The ligand–metal bifunctional rhenium catalysts [Re(H)(NO)(PR₃)(C₅H₄OH)] (R=iPr ( 5 a ), Cy ( 5 b )) were prepared from compounds 3 a and 3 b by silyl deprotection with TBAF and subsequent acidification of the intermediate salts [Re(H)(NO)(PR₃)(C₅H₄O)][NBu₄] (R=iPr ( 4 a ), Cy ( 4 b )) with NH₄Br. In nonpolar solvents, compounds 5 a and 5 b formed an equilibrium with the isomerized trans‐dihydride cyclopentadienone species [Re(H)₂(NO)(PR₃)(C₅H₄O)] ( 6 a,b ). Deuterium‐labeling studies of compounds 5 a and 5 b with D₂ and D₂O showed H/D exchange at the H_Re and H_O positions. Compounds 5 a and 5 b were active catalysts in the transfer hydrogenation reactions of ketones and imines with 2‐propanol as both the solvent and H₂ source. The mechanism of the transfer hydrogenation and isomerization reactions was supported by DFT calculations, which suggested a secondary‐coordination‐sphere mechanism for the transfer hydrogenation of ketones.     

Three New MOFs Induced by Organic Linker Coordination Modes: Gas Sorption,Luminescence, and Magnetic Properties

By using a new 4,6‐bis(imidazol‐1‐yl) isophthalic acid ligand (H₂bimip) with imidazolyl and carboxyl bifunctional groups, three new MOFs, [Co(bimip)(H₂O)_0.5] ? 0.5 H₂O ( 1 ), [Zn(bimip)] ( 2 ), and [Mn(bimip)(H₂O)₂] ? H₂O ( 3 ), have been solvothermally synthesized in different solvent systems. H₂bimip displays three different coordinated modes through the imidazolyl and carboxyl groups, and different cis–cis and trans–cis configurations, which result in distinct 3D topological frameworks: a (4,8)‐connected scu net for 1 ; a twofold interpenetrated (4,4)‐connected pts net for 2 ; and a four‐connected sra net for 3 . Compounds 1 and 3 show antiferromagnetic properties, and 2 emits strong solid‐state blue luminescence. Compound 1 shows good chemical stability in acidic and basic environments and in boiling water. Additionally, the polar channels in 1 , which are decorated by uncoordinated carboxylate O atoms and imidazolyl fragments, allow it to adsorb CO₂ molecules selectively over CH₄, and the CO₂ binding sites in the framework were distinguished by molecular simulations.     

Synthesis and Properties of New Thiacalixarene Derivatives with Palladium Ion

Three new thiacalix[4]arene derivatives, 5,11,17,23-tetra-tert-butyl-25,27-di(2-hydroxyethoxy)-26,28-dihydroxythiacalix-{}[4]arene (2), 5,11,17,23-tetra-tert-25, 26,27,28-tetrakis[(methylcarboxyl)methoxy]thiacalix[4]arene (3),5,11,17,23-tetra-tert-butyl-25,26,27,28-tetrakis(2-hydroxy-1-propanoxy)thiacalix[4]arene (4), were synthesized for the first time. The coordination properties of thiacalix[4]arene(1) and its derivatives (2 and 4) were investigated by detecting the interactions betweenthese compounds and two palladium complexes, cis-[Pd(en)(H₂O)₂]²⁺ and cis-[Pd(dtco-3-OH)(H₂O)₂]²⁺, by means of electrospray ionization mass spectrometry (ESI-MS) technique.     

Amidoliganden zum Aufbau von mehrkernigen Lanthanoidkomplexen

Amido Ligands for the Synthesis of Polynuclear Lanthanoid Complexes By 1 : 1 reaction of LnBr₃ with NaNHPh in THF the Rare-Earth Complexes [Ln₂Br₄(μ₂-NHPh)₂(thf)₅] (Ln = Sm ( 1 ), Ln = Gd ( 2 )) with two bridging anilido ligands are obtained. In the system LnBr₃/NaNHPh/(Me₂SiO)₃ the tetranuclear compounds [Ln₄(μ₄-O)(NHPh)₃(OSiMe₂NPh)₆Na₅(thf)₇] · THF (Ln = Gd ( 3 ), Ln = Yb ( 4 )) can be built up. They have a central μ₄-oxygene atom in the Ln₄-tetrahedron. It has an oxa-dimethylsilyl-N-phenylamido ligand over all edges and an anilido ligand on three vertexes. By this reaction small amount of [Na₄(thf)₆Yb₂(OSiMe₂NPhSiMe₂O)₂(OSiMe₂NPh)₂(NHPh)₂] ( 5 ) with a O- and N-bridged Yb–Na polyhedron and N-phenyl-bis(dimethylsilanolato)-ligands coordinating μ₂-η² with its oxygen atoms are obtained. Reaction of Lanthanideshalides with LiNH^tBu leads to dimeric complexes. The formation of bridging oxasilylamido ligands is also observed. The compound [Li₂Ln(OSiMe₂N^tBu)₂(HN^tBu)(thf)]₂ (Ln=Sm ( 6 ), Gd ( 7 ) and Yb ( 8 )) contains now an O- and N-bridged Ln–Li polyhedron. (Crystal Data of 1–8 see ‘‘Inhaltsverzeichnis”︁”︁).     

Kinetic study of the protonations and substitutions of different cobalt(III)–nta complexes

The behaviour of the Cobalt(III)–nta (nta = nitrilotriacetate) system in an acidic medium was investigated. The acid dissociation constant, pK _a1, of [(nta)(H₂O)Co(-OH)Co(H₂O)(nta)]^– was determined as 3.09(3) and the pK _a of the cis-[Co(nta)(H₂O)₂]/[Co(nta)(H₂O)(OH)]^– equilibrium was determined as 6.71(1). cis-[Co(nta)(H₂O)₂] undergoes ring-opening upon acidification below pH = 2.0. The formation of [Co( ³-nta)(H₂O)₃]⁺ was also studied. The substitutions between cis-[Co(nta)(H₂O)₂] and NCS^– ions were investigated in the pH = 2–7 ranges. [Co(nta) (H₂O)(OH)]^– reacts ca. 70 times faster at 24.7 °C with NCS^– ions than cis-[Co(nta)(H₂O)₂], indicating a cis-labilising effect of the OH^– ligand.     

Synthesis,crystal structures and xanthine oxidase inhibitory activities of two copper(II) complexes with Schiff bases

Two azido-coordinated Schiff base Cu(II) complexes with the formulae [Cu(L1)(N₃)]·MeOH and [Cu(L2)(μ_1,1-N₃)] _n , where L1 is the deprotonated form of 2-chloro-2-[(2-ethylaminoethylimino)methyl]phenol, and L2 is the deprotonated form of 2,4-dibromo-6-[(2-dimethylaminoethylimino)methyl]phenol, have been synthesized and characterized by physico-chemical and spectroscopic methods. The X-ray crystal structures of both complexes have been determined. The Cu atom in [Cu(L1)(N₃)]·MeOH is four-coordinate in a square planar geometry, while [Cu(L2)(μ_1,1-N₃)] _n is five-coordinate with a square pyramidal geometry. The molecules in [Cu(L1)(N₃)]·MeOH are linked by intermolecular O–H···O and N–H···O hydrogen bonds, forming dimers. The molecules in [Cu(L2)(μ_1,1-N₃)] _n are linked through end-on azido bridges, forming one-dimensional chains. The xanthine oxidase inhibitory activities of both complexes were evaluated.     

Complexes of cis -dihalogenorhenium(V) with iminophenol

Complexes cis-[ReOX₂(msa)(PPh₃)]?[X?=?Cl(1), I(2)] were prepared from trans-[ReOCl₃(PPh₃)₂] or trans-[ReOI₂(OEt)(PPh₃)²] with 2-(1-iminoethyl)phenol (Hmsa) in acetonitrile. An X-ray crystallographic study shows that the bonding distances and angles in 1 and 2 are nearly identical, and that the two halides in each complex are coordinated cis to each other in the equatorial plane cis to the oxo group. Rhenium(V) complexes with cis diiodides are rare. All bonding distances and angles are in the expected ranges.