Halogeno Ligands Research Articles

Reactions of Cadmium(II) Halides and Di-2-Pyridyl Ketone Oxime: One-Dimensional Coordination Polymers.

The coordination chemistry of 2-pyridyl ketoximes continues to attract the interest of many inorganic chemistry groups around the world for a variety of reasons. Cadmium(II) complexes of such ligands have provided models of solvent extraction of this toxic metal ion from aqueous environments using 2-pyridyl ketoxime extractants. Di-2-pyridyl ketone oxime (dpkoxH) is a unique member of this family of ligands because its substituent on the oxime carbon bears another potential donor site, i.e., a second 2-pyridyl group. The goal of this study was to investigate the reactions of cadmium(II) halides and dpkoxH in order to assess the structural role (if any) of the halogeno ligand and compare the products with their zinc(II) analogs. The synthetic studies provided access to complexes {[CdCl2(dpkoxH)∙2H2O]}n (1∙2H2O), {[CdBr2(dpkoxH)]}n (2) and {[CdI2(dpkoxH)]}n (3) in 50-60% yields. The structures of the complexes were determined by single-crystal X-ray crystallography. The compounds consist of structurally similar 1D zigzag chains, but only 2 and 3 are strictly isomorphous. Neighboring CdII atoms are alternately doubly bridged by halogeno and dpkoxH ligands, the latter adopting the η1:η1:η1:μ (or 2.0111 using Harris notation) coordination mode. A terminal halogeno group completes distorted octahedral coordination at each metal ion, and the coordination sphere of the CdII atoms is {CdII(η1 - X)(μ - X)2(Npyridyl)2(Noxime)} (X = Cl, Br, I). The trans-donor-atom pairs in 1∙2H2O are Clterminal/Noxime and two Clbridging/Npyridyl; on the contrary, these donor-atom pairs are Xterminal/Npyridyl, Xbridging/Noxime, and Xbridging/Npyridyl (X = Br, I). There are intrachain H-bonding interactions in the structures. The packing of the chains in 1∙2H2O is achieved via π-π stacking interactions, while the 3D architecture of the isomorphous 2 and 3 is built via C-H∙∙∙Cg (Cg is the centroid of one pyridyl ring) and π-π overlaps. The molecular structures of 1∙2H2O and 2 are different compared with their [ZnX2(dpkoxH)] (X = Cl, Br) analogs. The polymeric compounds were characterized by IR and Raman spectroscopies in the solid state, and the data were interpreted in terms of the known molecular structures. The solid-state structures of the complexes are not retained in DMSO, as proven via NMR (1H, 13C, and 113Cd NMR) spectroscopy and molar conductivity data. The complexes completely release the coordinated dpkoxH molecule, and the dominant species in solution seem to be [Cd(DMSO)6]2+ in the case of the chloro and bromo complexes and [CdI2(DMSO)4].

Anionic ligands tune the structural and catalytic properties of quinoxaline-based copper(II) complexes as mimetics of copper-containing oxidase protein

The hexadentate ligand containing quinoxaline backbone along with its Cu(II) -based complexes with various anionic ligands were synthesized and their structures were determined. Molecular formulae were assigned based on the data of both elemental analysis and the electrical conductivity in DMF solutions. Spectroscopic and magnetic measurements were performed to achieve the final structural properties. The exact geometry of the synthesized Cu(II) complexes was demonstrated by processing the PXRD data using a computer program specializing in the structural analysis of metallic complexes. The anionic ligands included in the complex molecule adjust the stereochemistry of the central Cu(II) ion. In this regard, the halogeno ligands direct the octahedral environment while the nitrato, acetato and perchlorato ligands adjust the dsp3 hybridization of the trigonal bipyramidal stereochemistry. Mimicry of copper oxidase proteins such as catechol oxidase and phenoxazine synthase has been studied. The oxidase biomimetic catalytic activity was tuned by the anionic ligands included in the Cu(II) oxidase mimics. Kinetic measurements allowed the determination of relevant parameters such as Vmax, kcat, KM and the ratio kcat/KM. The potential catalytic reaction sequences have been suggested based on the results of kinetic investigations. The driving force of the studied catalytic reactions was determined based on the electrochemical data and the impact of the driving force (λ or–ΔG°) on the catalytic activity was addressed.

Tunable magnetic anisotropy in luminescent cyanido-bridged {Dy2Pt3} molecules incorporating heteroligand PtIV linkers.

The interest in the generation of photoluminescence in lanthanide(III) single-molecule magnets (SMMs) is driven by valuable magneto-optical correlations as well as perspectives toward magnetic switching of emission and opto-magnetic devices linking SMMs with optical thermometry. In the pursuit of enhanced magnetic anisotropy and optical features, the key role is played by suitable ligands attached to the 4f metal ion. In this context, cyanido complexes of d-block metal ions, serving as expanded metalloligands, are promising. We report two novel discrete coordination systems serving as emissive SMMs, {[DyIII(H2O)3(tmpo)3]2[PtIVBr2(CN)4]3}·2H2O (1) and {[DyIII(H2O)(tmpo)4]2[PtIVBr2(CN)4]3}·2CH3CN (2) (tmpo = trimethylphosphine oxide), obtained by combining DyIII complexes with uncommon dibromotetracyanidoplatinate(IV) ions, [PtIVBr2(CN)4]2-. They are built of analogous Z-shaped cyanido-bridged {Dy2Pt3} molecules but differ in the coordination number of DyIII (C.N. = 8 in 1, C.N. = 7 in 2) and the number of coordinated tmpo ligands (three in 1, four in 2) which is related to the applied solvents. As a result, both compounds reveal DyIII-centred slow magnetic relaxation but only 1 shows SMM character at zero dc field, while 2 is a field-induced SMM. The relaxation dynamics in both systems is governed by the Raman relaxation mechanism. These effects were analysed using ac magnetic data and the results of the ab initio calculations with the support of magneto-optical correlations based on low-temperature high-resolution emission spectra. Our findings indicate that heteroligand halogeno-cyanido PtIV complexes are promising precursors for emissive SMMs with the further potential of sensitivity to external stimuli that may be related to the lability of the axially positioned halogeno ligands.

Halogeno Ligand‐Substitution Reactions of Ruthenium Complexes Bearing Ethylbis(2‐pyridylmethyl)amine to Synthesize New Complexes

Halogeno ligand‐substitution reactions of trihalogenoruthenium(III) complexes bearing ethylbis(2‐pyridylmethyl)amine (ebpma), fac‐[RuIIIX3(ebpma)] (X = Cl; [1Cl], Br; [1Br]) were investigated to derive various complexes of desired properties and reactivities. The number of substitution of halogeno ligand (n) was controlled. Through the reaction of [1Cl] with sulfuric acid in acetonitrile, a mono‐substituted acetonitrileruthenium(III) complex fac‐[RuIIICl2(NCCH3)(ebpma)]+ (n = 1, [2]+) was obtained, while the one‐electron reduction reactions of the Ru(III) center of [1X] in a hydrophobic solution or in a water‐containing solution with Lewis base afforded fac‐[RuIIX(L)2(ebpma)]+ (n = 2, L = CH3CN; [3X]+, C5H5N; [5X]+) or fac‐[RuII(L)3(ebpma)]2+ (n = 3, L = CH3CN; [4]2+, C5H5N; [6]2+, NH3; [7]2+), respectively. The number of dissociating chlorido and the kind of incoming ligand could be controlled as expected in these synthetic strategies. The structures, redox behaviors and spectroscopic properties of the obtained ruthenium complexes were studied.

Catalytic reactivity of the complexes [Pd{(Ph2P)2N(tBu)-P,P´}X2], X = Cl, Br, I, in the Suzuki-Miyaura C−C coupling reaction: Probing effects of the halogeno ligand X− and the ligand's tBu group

The synthesis, as well as the spectroscopic and structural characterization of three analogous palladium(II) complexes, [Pd{(Ph2P)2N(tBu)-κ2P,P´}X2], X = Cl, Br, I, is presented. X-ray crystallography studies revealed a similar square planar PdP2X2 first coordination sphere among the three complexes. The catalytic reactivity of these complexes was tested in the Suzuki-Miyaura coupling reaction, showing that the X = Cl, Br, complexes are more active than the X = I analogue. The differences in the catalytic reactivity within this series of complexes, as well as comparisons with similar palladium(II) catalysts reported in the literature, are discussed with respect to the different electronegativity of the three halogens and the strong +I inductive effect of the ligand's tBu group.

Synthesis of Heterobimetallic Complexes by Coordination of Rhodium(III) and Iridium(III) Poly-N,O-NHC Complexes to Silver(I), Copper(II), and Zinc(II)

The reaction of [RhCl2(Cp*)]2 with 2-trimethylsiloxyphenyl isocyanide (1) led to the mononuclear diisocyanide complex [RhCl(Cp*)(1)2]. Cleavage of the Si–O bonds of the coordinated isocyanide ligands with a catalytic amount of KF and H2O gave the neutral rhodium(III) complex [RhCl(Cp*)(NH,O-NHC)(N,O-NHC)] ([2]) bearing a C2-metalated N,O-benzoxazolinato ligand and an NH,O-benzoxazolin-2-ylidene ligand. In the presence of AgBF4 the same reaction sequence with [MCl2(Cp*)]2 (M = Rh, Ir) and 1 led to the removal of all halogeno ligands and formation of the complexes [M(Cp*)(NH,O-NHC)(N,O-NHC)2] (M = Rh, [3]; M = Ir, [4]) bearing one C-metalated NH,O-NHC benzoxazolin-2-ylidene and two C-metalated N,O-benzoxazolinato ligands. Deprotonation of the remaining N–H function in complexes [3] and [4] generated complexes with three amido donor functions which act as tripodal metalloligands for the coordination to additional transition metals such as AgI, CuII, and ZnII, thus allowing the preparation of the polynuclear ...

Systematic Modulation of the Fluorescence Brightness in Boron-Dipyrromethene (BODIPY)-Tagged N-Heterocyclic Carbene (NHC)-Gold-Thiolates.

Five different highly fluorescent boron-dipyrromethene (BODIPY)-tagged N-heterocyclic carbene NHC-gold halide complexes were synthesized. The substitution of the halogeno ligand by 4-substituted aryl thiolates leads to a decrease in the brightness of the complexes. This decrease depends on the electronic nature of the thiols, being most pronounced with highly electron-rich thiols (4-R=NMe2 ). The brightness of the gold thiolates also depends on the distance between the sulfur atom and the BODIPY moiety. The systematic variation of the electron density of [(NHC-bodipy)Au(SC6 H4 R)] (via different R groups) enables the systematic variation of the fluorescence brightness of an appended BODIPY fluorophore. Based on this and supported by DFT calculations, a photoinduced electron-transfer quenching appears to be the dominant mechanism controlling the brightness of the appended BODIPY dye.

Neutral Pentacoordinate Halogeno‐ and Pseudohalogenosilicon(IV) Complexes with a Tridentate Dianionic O,N,O or N,N,O Ligand: Synthesis and Structural Characterization in the Solid State and in Solution

AbstractA series of neutral pentacoordinate silicon(IV) complexes with an SiFO2NC, SiBrO2NC, SiO2NC2, SiO2N2C, SiFON2C, SiBrON2C, SiON2C2, or SiON3C skeleton was synthesized and structurally characterized by multinuclear NMR spectroscopy in the solid state and in solution and by single‐crystal X‐ray diffraction. The compounds studied contain a tridentate dianionic O,N,O or N,N,O ligand, a phenyl ligand, and a (pseudo)halogeno ligand (F, Br, CN, N3, NCS). The structures, NMR spectroscopic parameters, and chemical properties of these silicon(IV) complexes were compared with those of related compounds that contain an analogous tridentate dianionic S,N,O ligand instead of the O,N,O or N,N,O ligand (comparison of S/O/NMe analogues). In addition, two cationic pentacoordinate silicon(IV) complexes with an SiO2N2C and SiON3C skeleton, respectively, were synthesized (isolated as iodides) and structurally characterized. These compounds contain a tridentate O,N,O or N,N,O ligand, a phenyl ligand, and an acetonitrile ligand. The experimental investigations reported in this article were complemented by computational studies to better understand the different properties of some of the S/O/NMe analogues studied.

Novel neutral hexacoordinate benzamidinatosilicon(iv) complexes with SiN3OF2, SiN3OCl2, SiN3OBr2, SiN5O and SiN3O3 skeletons

The neutral pentacoordinate monoamidinatosilicon(IV) complex 1 (SiN(2)Cl(3) skeleton) and the neutral hexacoordinate monoamidinatosilicon(IV) complexes 2-9 (SiN(3)OF(2), SiN(3)OCl(2), SiN(3)OBr(2), SiN(5)O and SiN(3)O(3) skeletons) were synthesised and characterised by elemental analyses, single-crystal X-ray diffraction (except for 1) and NMR spectroscopy in the solid state and in solution. Compounds 2-9 contain one bidentate monoanionic N,N'-diisopropylbenzamidinato ligand, one bidentate monoanionic ligand derived from 8-hydroxyquinoline and (i) two identical monoanionic ligands (F, Cl, Br, N(3), NCO, NCS, OSO(2)CF(3)) or (ii) one bidentate dianionic benzene-1,2-diolato ligand. The dynamic behavior of 2-4 (SiN(3)OX(2) skeleton; X = F, Cl, Br) and 9 (SiN(3)O(3)) in solution was studied by multinuclear variable-temperature NMR experiments. Compound 1 was synthesised by reaction of SiCl(4) with the corresponding lithium amidinate, and compound 2 was obtained by reaction of 1 with 8-hydroxyquinoline and triethylamine. Compound 2 served as the starting material in the syntheses of 3-9, in which the two chloro ligands of 2 were substituted by two identical (pseudo)halogeno ligands, two trifluoromethanesulfonato ligands or one benzene-1,2-diolato ligand. Compounds 3 and 4 contain the novel SiN(3)OBr(2) and SiN(3)OF(2) skeletons, while compounds 5-7 are the first neutral hexacoordinate silicon(IV) complexes with an SiN(5)O skeleton.

Oxorhenium(V) Complexes with 2,3‐Dihydroxynaphthalene

Abstract2,3‐Dihydroxynaphthalene (H2dhn) reacts with [ReOCl3(PPh3)2] or [ReOBr3(PPh3)2] in a 1:1 molar ratio with formation of the isostructural complexes [ReOCl2(PPh3)2(Hdhn)] (4) and [ReOBr2(PPh3)2(Hdhn)] (5). They have distorted octahedral coordination spheres with the halide and the triphenylphosphine ligands arranged in equatorial trans positions to each other. The Hdhn– ligand coordinates monodentately in trans position to the oxo ligand. Intramolecular hydrogen bonds between the Hdhn– and the halogeno ligands stabilize this coordination mode. The products represent the first examples of oxorhenium(V) complexes with monodentate catecholate‐type ligands.

Neutral Pentacoordinate Halogeno- and Pseudohalogenosilicon(IV) Complexes with an SiSONCX Skeleton (X=F, Cl, Br, I, N, C): Synthesis and Structural Characterization in the Solid State and in Solution

A series of neutral pentacoordinate silicon(IV) complexes with an SiSONCX skeleton (X=F, Cl, Br, I, N, or C) was synthesized and structurally characterized by multinuclear solution-state and solid-state NMR spectroscopy and single-crystal X-ray diffraction. These compounds contain an identical tridentate dianionic S,N,O ligand, a monodentate (pseudo)halogeno ligand (F, Cl, Br, I, NCS, N(3), or CN), and a monodentate organyl ligand (methyl, phenyl, 4-(trifluoromethyl)phenyl, or pentafluorophenyl). For most of these compounds, a dynamic equilibrium between the pentacoordinate silicon(IV) complex and two isomeric tetracoordinate silicon species in solution was observed. Most surprisingly, comparison of two series of analogous compounds containing fluoro, chloro, bromo, or iodo ligands demonstrated that pentacoordination in these series of silicon(IV) complexes is favored in the rank order I approximately Br>Cl>F; i.e., increasing the softness of the halogeno ligand favors pentacoordination.

Platinum complexes with diamino-substituted phosphorus ligands: Synthesis, characterization, and their reactivity with a Lewis acid

Abstract Reaction of dialkyl- or diaryl-platinum complexes PtR2(cod) (cod = η2, η2-1,5-cyclooctadiene, R = Me, p-tol) with diamino-substituted phosphorus ligands P(NMeCH2)2(R′) (R′ = OMe, NEt2) produced neutral complexes, cis-[Pt(R)2{P(NMeCH2)2(R′)}2]. On the other hand, reaction of dihalogeno platinum complex PtX2(cod) (X = Cl, I) with P(NMeCH2)2(OMe) yielded a cationic complex [PtX{P(NMeCH2)2(OMe)}3]X. A platinum complex having both methyl and halogeno ligands, PtMeX(cod), reacted with P(NMeCH2)2(OMe) to give a cationic methyl complex [PtMe{P(NMeCH2)2(OMe)}3]X, by contrast, it reacted with P(NMeCH2)2(NEt2) to yield a neutral methyl complex [PtMeX{P(NMeCH2)2(NEt2)}2]. Reaction of [PtMe{P(NMeCH2)2(OMe)}3]X with BF3·OEt2 and then NaBPh4 afforded [PtX{P(NMeCH2)2(OMe)}3]BPh4, showing preferential Me group abstraction on the Pt center rather than the OMe abstraction on the phosphorus atom, followed by the coordination of X to the Pt center. All new complexes were fully characterized using 1H, 13C{1H}, and 31P{1H} NMR measurements and elemental analyses. In addition, structures of several complexes were determined by single crystal X-ray diffraction studies.

Mono- and bimetallic ethylene polymerization catalysts having an azanickellacyclopentene skeleton

A series of azanickellacyclopentene complexes having iodo, bromo, chloro, or triflate ligand on the Ni center were prepared, and are subjected to studies on ethylene polymerization catalysis. Activity of these mononuclear azanickellacyclopentene complexes was increased in the order, Ni–Cl < Ni–I ≈ Ni–Br < Ni–OTf; this is explained by the performance of (pseudo)halogeno ligand as a leaving group from the nickel center. Methylalminoxane (MAO) and inexpensive AlEt 2Cl can be used as the cocatalyst. Mechanistic consideration suggested the involvement of neutral Ni-alkyl intermediates as proposed in the SHOP type catalytic system. Interestingly, the catalytic activity is significantly increased by incorporating the second metals into the diimino moiety of mononuclear complex. Two factors should be considered to explain this activity enhancement. One is the increased rigidity of the azanickellacyclopentene ligand backbone, and the other is the possibility of the presence of the two active centers in one molecule.

Photophysical properties of copper(I) and zinc(II) complexes containing phosphinoquinoline ligands

Several copper(I) and zinc(II) complexes with 8-(diphenylphosphino)quinoline (PPh 2qn) or 8-diphenylphosphinoquinaldine (PPh 2qna) have been prepared. These ligands contain both imine and phosphine moieties, which can act as coordinating groups. X-ray analysis of the Cu(I) complexes reveals that [Cu(PPh 2qn) 2]PF 6 ( Cu-1) and [Cu(PPh 2qn) 2]PF 6 ( Cu-2), coordinated by two PPh 2qn and PPh 2qna ligands respectively, are obtained. In the Zn(II) complexes, a structural study shows that [ZnCl 2(PPh 2qn)] ( Zn-1), [ZnBr 2(PPh 2qn)] ( Zn-2) and [ZnI 2(PPh 2qn)] ( Zn-3) are coordinated by one PPh 2qn ligand and two of the corresponding halogeno ligands (Cl −, Br − and I −). In the solid state Cu-1 and Cu-2 show luminescence which is assigned to a 3MLCT transition involving π∗ of the quinoline group, as shown in the [Cu(dmp)(diphosphine)] + complexes; due to the reduced bulkiness of the coordination sphere around the copper atom, no emission is observed in solution. Zn-1 shows a similar emission band to that of free PPh 2qn at both room temperature and 77 K. It suggests the emission bands should be assigned to a ligand-centered (LC) transition. In the solid state, it is found that the emissive energy of the complexes shift to lower energy and the energy depends on the halogeno ligands in the zinc complexes.

Rhenium chelate complexes with maltolate or kojate

Novel rhenium complexes containing the maltolate (mal) or kojate (koj) anions as chelating ligands have been synthesized: [ReOCl(mal) 2] ( 1), [ReOCl 2(mal)(PPh 3)] ( 2), [ReOBr 2(mal)(PPh 3)] ( 3), [ReOCl 2(koj)(PPh 3)] ( 4) and [ReOBr 2(koj)(PPh 3)] ( 5). The products have been characterized by FTIR, 1H, 13C, and 31P NMR spectroscopies and elemental analysis. The crystal and molecular structures of all complexes were determined. Complex 1 crystallizes monoclinic, space group C2/ c, Z = 8. It contains two O,O′-bidentate maltolate ligands and one chloro ligand at the (ReO) 3+ unit, so that a distorted octahedral geometry is adopted by the six-coordinated rhenium(V) center. The chloro ligand occupies a cis position to the oxo ligand. Complexes 2 and 3 are isostructural and crystallize orthorhombic, space group Pbca and Z = 8. The isostructural complexes 4 and 5 crystallize monoclinic, space group P2 1/ n and Z = 4. In complexes 2– 5, the (ReO) 3+ unit is coordinated by a monoanionic O, O-bidentate unit of the maltolate ( 2 and 3) or kojate ( 4 and 5) ligand, one triphenylphosphine and two halogeno ligands (Cl in 2 and 4; Br in 3 and 5), with the rhenium(V) center in a distorted octahedral environment. The halide ligands are in cis positions to each other.

Observation of Halide-Induced Conformational Conversion of Dinuclear Copper Complexes Having a Tetradentate Polypyridine Ligand with a p-Xylene Backbone

A dinucleating ligand consisting of thiopyridyl groups appended to a p-xylene backbone reacts with copper(I) halides to afford dinuclear copper complexes with terminal halogeno ligands, which are in equilibrium with bridging halogeno dicopper complexes formed by rearrangement and loss one of the terminal halogeno ligands. The identity of the products was confirmed by using 1 HNMR spectroscopy, electrospray ionization mass spectrometry, and X-ray structure analyses.

Syntheses and activity of some platinum(IV) complexes with N-methyl derivate of glycine and halogeno ligands against HeLa, K562 cell lines and human PBMC

Four platinum(IV) complexes, trans, trans-dichlorobis( N, N-dimethylglycinato)platinum(IV), trans, trans-[Pt(dmgly) 2Cl 2] ( 1) and trans, trans-dibromobis( N, N-dimethylglycinato)platinum (IV), trans, trans-[Pt(dmgly) 2Br 2] ( 2), as well as, trans, trans-dichlorobis( N-methylglycinato)platinum(IV), trans, trans-[Pt(sar) 2Cl 2] ( 3) and trans, trans-dibromobis( N-methylglycinato)platinum(IV), trans, trans-[Pt(sar) 2Br 2] ( 4) (with configuration index for all complexes OC-6–14), were synthesized and characterized by elemental analysis, infrared and 1H NMR spectroscopy. In the aim to assess the selectivity in the antitumor action of these complexes, the antiproliferative action of these compounds was determined to human adenocarcinoma HeLa cells; to human myelogenous leukemia K562 cells and to normal immunocompetent cells; i.e., on human PBMC. The details of the crystal structure synthesized trans, trans-[Pt(sar) 2Br 2] complex were also reported here. In the crystal structure of trans, trans-[Pt(sar) 2Br 2], the Pt(IV) ion had a deformed octahedral coordination with both N-methylglycinates and bromides bonded trans to one another and with the N–Pt–Br bond angles of 84.1(4) and 95.9(4)°. The trans, trans-[Pt(sar) 2Br 2] complex molecules form 2D-layers with multiple N–H⋯O and C–H⋯O hydrogen bonds.

Activity of some platinum(II/IV) complexes with O, O- n-butyl-and O, O- n-pentyl-ethylenediamine- N, N′-di-3-propanoate and halogeno ligands against HeLa and K562 cell lines and human PBMC

This paper reports on syntheses and characterization of chlorotribromo( O, O- n-butyl-ethylenediamine- N, N′-di-3-propanoate)platinum(IV) [II], dichlorodiiodo( O, O- n-butyl-ethylenediamine- N, N′-di-3-propanoate)platinum(IV) [III], and dichloro( O, O- n-butyl-ethylenediamine- N, N′-di-3-propanoate)platinum(II) [V] complexes, with the formulae [Pt(dbeddp)Br 3Cl], [Pt(dbeddp)Cl 2I 2] and [Pt(dbeddp)Cl 2], respectively. The complexes were characterized by elemental analysis, infrared, 1H and 13C NMR spectroscopy and electrospray mass spectrometry. In the aim to assess the selectivity in the antitumor action of these complexes, as well, as tetrachloro( O, O- n-butyl-ethylenediamine- N, N′-di-3-propanoate)platinum(IV) [I] and tetrachloro( O, O- n-pentyl-ethylenediamine- N, N′-di-3-propanoate)platinum(IV) [IV], the antiproliferative action of these compounds was determined to human adenocarcinoma HeLa cells, to human myelogenous leukemia K562 cells and to normal immunocompetent cells, i.e., on human peripheral blood mononuclear PBMC cells.

Structure of Halogenophosphorincopper(I) Complexes in Solid State and Solution: Study with X-ray Crystallography and CP/MAS- 31P{ 1H}-NMR Spectroscopy

Halogenophosphorincopper(I) complexes [Cu(dmppn)X] (X=Cl ( 1), Br ( 2), I ( 3)) have been synthesized from 4,5-dimethyl-2-phenylphosphorin (dmppn) with copper(I) halide CuX (X=Cl, I) or copper(II) dihalide CuX 2 (X=Cl, Br). The crystal structure of 3 was determined by single crystal X-ray crystallography and showed supramolecular structure so called an infinite stair polymer. This complex is the only one for the infinite stair polymer of halogenocopper(I) complex with phosphorus ligand to the best of our knowledge. The chemical shifts for these complexes were observed to be 159.3( 1), 158.1( 2), and 151.2 ppm( 3) by CP/MAS– 31P{ 1H} NMR spectroscopy in the solid state and they showed significant upfield shifts over 20 ppm relative to that of the free ligand in CDCl 3. These upfield shifts indicate that the phosphorin undergoes strong π-back donation from the copper(I) center and the magnitudes of the upfield shifts for the complexes showed an obvious increase in order of I>Br>Cl. This trend indicates that degree of the π-back donation is influenced by the donor character of the halogeno ligand through the copper–halogen bonding. The copper center in these complexes was further determined to have a four-coordination in a distorted tetrahedron with CP/MAS– 31P{ 1H}–NMR data and this result suggests that three complexes were formed the supramolecular structure of the infinite stair polymer in the solid state.

Normal coordinate analyses of ruthenium–sulfur dioxide complexes

Ambient- and low-temperature IR, FIR and FT-Raman spectra of the complexes trans-[RuX(NH/D 3) 4SO 2]X (X=Cl ( 1/ 1D), Br ( 2/ 2D), I ( 3/ 3D)) were measured to provide the bases for normal coordinate analyses (NCA). Further, X-ray structure analyses of 1– 3 yielded the required bonding parameters and justify the assumption of an idealized symmetry C 2v- mm2 for the cations. In accordance with the results of the structure determinations, the NCA calculations show an increasing trans-influence of the halogeno ligand on the Ru–S bond in the series Cl<Br<I. Formerly estimated force constants f r(RuN) are confirmed and neglect of cis-interactions is justified. Inspections of the eigenvalues and the potential energy distributions show an intense mixing of valence and deformation vibrations in symmetry species A 1.