Assignment of absolute configuration at phosphorus of P-chiral diastereomers of deoxyribonucleoside methanephosphonamidates by means of NMR spectroscopy

Recently, we have prepared a novel class of DNA analogues containing the [3′-NH-P(CH₃)(O)-O-5′] methanephosphonamidate linkage. Synthesis of such analogues requires preparation of the dinucleoside methanephosphonamidates N×N, where N is a 2′-deoxyribonucleoside moiety and × is the methanephosphonamidate linkage. Dimers T×T and C×T were obtained in a non-stereospecific manner giving rise to a pair of P-chiral diastereomers. Such diastereomers were effectively separated into fast and slow migrating ones by means of chromatographic methods (TLC). As described in our previous work (Nawrot et al. Nucleic Acids Res.1998, 26, 2650), the stereochemistry of the phosphorus chiral center of T×T fast migrating diastereomer is R_P and of T×T slow migrating diastereomer is S_P, as established by means of 2D ROESY experiments. Here we describe assignment of the absolute configuration at the phosphorus center of fast and slow migrating diastereomers of C×T dimer. The 2D ROESY sequence with phosphorus decoupling during acquisition used in these measurements allowed observation of the P-Me group as a singlet instead of a ¹H-³¹P-coupled doublet. The apparent advantage of this approach was a much better signal to noise ratio and improved resolution in the F1 dimension. For the fast migrating C×T diastereomer an R_P and for slow migrating C×T diastereomer an S_P configuration was assigned. Conformational analysis of both pairs of diastereomers T×T and C×T indicates significant differences in sugar ring puckering, which strongly depend on the nature of the nucleobase at the 5′-terminus of the dimer. The ribose rings of the 3′-amino-2′,3′-dideoxycytidine moiety of both diastereomers of C×T adopt predominantly a C3′-endo (North) conformation, while thymine-substituted ribofuranoses originating either from C×T or T×T dimers prefer a C2′-endo (South) conformation.     

Synthesis,characterization and spectroscopic studies of a new ligand [N′-(2-methoxybenzoyl)hydrazinecarbodithioate] ethyl ester and its Mn(II) and Cd(II) complexes: X-ray structural study of Mn(II) complex

A new dithioligand [N′-(2-methoxybenzoyl)hydrazinecarbodithioate] ethyl ester (H₂mbhce, 1) formed complexes [M(Hmbhce)₂]_n {M = Mn(II), Cd(II)} which have been characterized with the help of elemental analyses, magnetic susceptibility measurements, IR, UV–Vis, ¹H and ¹³C NMR and mass spectrometry. [Mn(Hmbhce)₂]_n (2) crystallized in monoclinic system with space group P₂₁/n. In the polymeric structure of 2, the ligand acts as an uninegative tridentate N(1), O(1), S(3) donor and forms a five membered chelate ring with N(1), C(2) and O(1). The intermediate bond lengths (between single and double bond distances) O(1)–C(2) = 1.241(3), N(2)–C(2) = 1.325(3), N(1)–N(2) = 1.393(2), N(1)–C(8) = 1.311(3) ? and C(8)–S(3) = 1.704(2) Å suggest considerable delocalization of charge which develops slightly aromatic character in the chelate ring.     

Silver(I) complexes of bis[2-(diphenylphosphino)phenyl] ether

The reaction of AgOTf in dichloromethane with bis(2-(diphenylphosphino)phenyl) ether (DPEphos) in an equimolar ratio afforded a dinuclear complex [Ag₂(κ²-P,P′-DPEphos)₂(μ-OTf)₂] (1), whereas the similar reaction in a 1:2 molar ratio resulted in the formation of a bis-chelating complex [Ag(κ²-P,P′-DPEphos)₂][OTf] (2). The silver(I) complex 1 was obtained as a dimer, in which two silver atoms are bridged by two triflate groups to form three adjacent eight-membered spirocyclic rings. The mixed-ligand complex [Ag(κ²-P,P′-DPEphos)(2,2′-bpy)][OTf] (3) was obtained in the reaction of 1 in dichloromethane with 2,2′-bipyridine. The crystal structures of complexes 1–3 were determined by single crystal X-ray analyses.     

1D coordination polymers of silver(I) and copper(II) based on bis(N-heterocyclic carbene) ligands: Synthesis and structural studies

The alkyl chain-linked diimidazolium (or dibenzimidazolium) salts, 1,1′-diethyl-4,4′-tetramethylene-diimidazolium-diiodide (L¹H₂·I₂) and 1,1′-diethyl-3,3′-trimethylene-dibenzimidazolium-diiodide (L²H₂·I₂), and their silver(I) and copper(II) coordination polymers, [L¹AgI]_n (1) and [L²Cu₂I₄]_n (2), have been prepared and characterized. Complex 1 is a 1D helical polymer generated by bidentated carbene ligands (L¹) and Ag(I) atoms. The 1D polymer of 2 is formed by bidentated carbene ligands (L²) and coplanar quadrilateral Cu₂I₂ units. 3D supramolecular frameworks in the crystal packings of 1 and 2 are formed via intermolecular weak interactions, including C–H···π contacts, π–π interactions and C–H···I hydrogen bonds.     

From neutral iminophosphoranes to multianionic phosphazenates. The coordination chemistry of imino-aza-P(V) ligands

This review deals with the chemistry and coordination behaviour of imino-aza phosphorus(V) ligands focussing on s- and p-block as well as Group 11 and 12 metal complexes. Imino phosphorus(V) ligands contain one or more terminal RNP-units, which include iminophosphoranes R₃PNR′, monoanionic diiminophosphinates [R₂P(NR′)₂]⁻, dianionic triiminophosphonates [RP(NR′)₃]²⁻ and trianionic tetraiminophosphates [P(NR′)₄]³⁻. Aza-phosphorus(V) ligands feature bridging PNP units, which include cyclic and polymeric phosphazenes [R₂PN]_n. Imino-aza- phosphorus(V) ligands containing both imino and aza functions include linear diiminodiphosphazenates [N{R₂P(NR′)₂}₂]⁻ and multianionic poly(imino) cyclophosphazeantes such as [N₄{RP(NR′)}₄]⁴⁻ and [N₃{P(NR′)₂}₃]⁶⁻. Imino-aza phosphorus(V) ligands are assembled of three basic building blocks: the cationic tetravalent phosphonium centre (P), the anionic divalent amido function (N) and the terminally arranged R-group. The overall negative charge Z of the resulting ligand system is equal to the difference between the number of P and the number of N-centres: Z=n(P)n(N). Imino-aza phosphorus(V) ligands are electron rich N-donor ligands which co-ordinate via both N(imino) and N(aza) functions and have been applied in numerous metal complexes in order to stabilise low coordination numbers, unusual oxidation states and bonding modes or serve as ligands in homogeneous catalysis. The R-group provides both steric bulk and solubility in non-polar solvents. Multianionic phosphazenates feature a polydentate ligand surface, which facilitates an extremely high metal load. PN units of iminophosphoranes and phosphazenes have acceptor properties and enhance the acidity of α-alkyl and ortho-aryl protons. Deprotonation of P-alkyl and P-aryl iminophosphoranes give ligand systems featuring C,N chelating sites, which are also discussed.     

Synthesis and structure of diamine bis(phenolate) complexes containing the Ti(OEt)–O–Ti(OEt) function

Reaction of diamine-bis(phenol) ligands containing a mixture of N-methyl and N,N′-dimethyl-N,N-bis(2-hydroxy-3,5-dimethylbenzyl)ethylenediamine, H₂L¹ and H₂L³, with [Ti(OCHMe₂)₄ in absolute ethanol under reflux without exclusion of air and moisture gives [(L¹)Ti (OEt–O–Ti(OEt)(L¹)] (1). [(L³)Ti(OEt)–O–Ti(OEt)(L³)] (2) forms when the remaining solution containing [(L³)Ti(OEt)₂] (3) (characterised by X-ray crystallography) is hydrolysed with H₂O. For the N-methyl and N,N′-dimethyl ligand mixture H₂L² and H₂L⁴, which contain tert-butyl groups on the ortho-positions of the aryl rings, [(L²)Ti(OEt)–O–Ti(OEt)(L²)] (4) forms much more slowly and [(L⁴)Ti(OEt)₂] (5) does not hydrolyse when H₂O is added. When the N-protonated ligand N,N-bis(2-hydroxy-3-methyl-5-tert-butylbenzyl)ethylenediamine, H₂L⁵, is used, rapid hydrolysis to two isomers of [(L⁵)Ti(OEt–O–Ti(OEt)(L⁵)] (6) occurs without addition of water. For N,N-bis(2-hydroxy-3,5-di-tert-butylbenzyl)ethylenediamine, H₂L⁶, hydrolysis to [(L⁶)Ti(OEt)–O–Ti(OEt)(L⁶)] (7) occurs slowly when H₂O is added. For pendant NMe₂ ligand N,N-dimethyl-N′,N′-bis(2-hydroxy-3-methyl-5-tert-butylbenzyl)ethylenediamine, H₂L⁷, the hydrolysis reaction readily gives [(L⁷)Ti(OEt)–O–Ti(OEt)(L⁷)] (8) for which an X-ray crystal structure was obtained. The ortho-tert-butyl ligand derivative H₂L⁸ formed a complex analysing as [(L⁸)Ti(OEt)–O–Ti(OEt)(L⁸)] (9) which could not be studied further due to insolubility. Pendant pyridine ligand N-(2-pyridylmethyl)-N,N-bis(2′-hydroxy-3′-methyl-5′-tert-butylbenzyl)amine, H₂L⁹, apparently forms isomers of [(L⁹)Ti(OEt)–O–Ti(OEt)(L⁹)] and possibly [{(L⁹)Ti(O)}₂] from [(L⁹)Ti(OEt)₂] (10). The ortho-tert-butyl ligand derivative H₂L¹⁰ formed [(L¹⁰)Ti(OEt)–O–Ti(OEt)(L¹⁰)] (11) for which an X-ray crystal structure was obtained.     

Coordination polymers with the chiral ligand N-p-tolylsulfonyl-l-glutamic acid: Influence of metal ions and different bipyridine ligands on structural chirality

Four new polymers, namely [Ni(-tsgluO)(2,4′-bipy)₂(H₂O)₂]_n·5nH₂O (1), [Co(-tsgluO)(2,4′-bipy)₂(H₂O)₂]_n·5nH₂O (2), [Ni(-tsgluO)(4,4′-bipy)]_n·0.5nH₂O (3), and [Co(-tsgluO)(4,4′-bipy)]_n·0.5nH₂O (4), where tsgluO²⁻=(+)-N-p-tolylsulfonyl-l-glutamate dianion, 2,4′-bipy=2,4′-bipyridine, and 4,4′-bipy=4,4'-bipyridine, have been prepared and structurally characterized. Compounds 1 and 2 are isostructural and mononuclear, and crystallize in the acentric monoclinic space group Cc, forming 1D chain structures. Compound 3 is also mononuclear, but crystallizes in the chiral space group P2₁, forming a homochiral 2D architecture. In contrast to the other complexes, compound 4 crystallizes in the space group P−1 and is composed of binuclear [Co₂O₆N₂]_n⁴⁻ units, which give rise to a 2D bilayer framework. Moreover, compounds 1, 2, and 4 self-assemble to form 3D supramolecular structures through π-π stacking and hydrogen-bonding interactions, while compound 3 is further hydrogen-bonded to form 3D frameworks. We have demonstrated the influence of the central metal and bipyridine ligands on the framework chirality of the coordination complexes.     

Polymeric Zn(II) and Cu(II) complexes with exobidentate bridging l-tyrosine: Synthesis,structural and spectroscopic properties

A novel zinc(II) polymeric complex of the formula {[Zn(tyr)₂(H₂O)]H₂O}_n (1) containing l-tyrosine (tyr) was prepared in the crystalline form and characterized by X-ray diffraction, NIR–Vis–UV electronic and IR–FIR vibrational spectroscopy methods. Additionally, for the [Cu(tyr)₂]_n (2) polymer, the vibrational, electronic, EPR spectroscopic and magnetic properties were studied. l-tyrosine in coordination polymers acts as a N,O-bidendate ligand and presents exobidentate bridging with a μ-carboxyl group. The μ-carboxyl exobidentate bridging coordination mode leads to a one-dimensional chain structure. The ZnN₂O₃O′ chromophore has an elongated pseudo-octahedral geometry (1), whereas the CuN₂O₂O′ (2) chromophore presents a distorted square-pyramidal environment with τ = 0.19 around the Cu²⁺ ion.     

A computational study on mixed-ligand N2P3 donor-set iron(II) and ruthenium(II) classical and non-classical hydrides

Iron and ruthenium classical and non-classical hydrides of the type [MH(N–N)P₃]⁺ and [M(η²-H₂)(N–N)P₃]²⁺ {M = Fe, Ru; N–N = 2,2′-bipyridine (bpy), 1,10-phenanthroline (phen); P = phosphites} were reported in 2004 together with an evaluation of the pseudo-aqueous pK_a values of the η²-H₂ complexes. The non-classical hydrides, even if doubly charged, showed a relatively low acidity, their pK_a values ranging between −5.4 and −4.3. Moreover, ruthenium(II) derivatives showed to be more acidic than the corresponding iron(II) complexes. Information about the structural and electronic proprieties of complexes of this type, which allowed to better understand the role of both the metal centres and the ancillary ligands in the acidity of the co-ordinated hydrogen molecule, was obtained on the basis of DFT B3LYP calculations.     

Development of a ratiometric time-resolved luminescence sensor for pH based on lanthanide complexes

Time-resolved luminescence bioassay technique using lanthanide complexes as luminescent probes/sensors has shown great utilities in clinical diagnostics and biotechnology discoveries. In this work, a novel terpyridine polyacid derivative that can form highly stable complexes with lanthanide ions in aqueous media, (4′-hydroxy-2,2′:6′,2′′-terpyridine-6,6′′-diyl) bis(methylenenitrilo) tetrakis(acetic acid) (HTTA), was designed and synthesized for developing time-resolved luminescence pH sensors based on its Eu³⁺ and Tb³⁺ complexes. The luminescence characterization results reveal that the luminescence intensity of HTTA–Eu³⁺ is strongly dependent on the pH values in weakly acidic to neutral media (pK_a = 5.8, pH 4.8–7.5), while that of HTTA–Tb³⁺ is pH-independent. This unique luminescence response allows the mixture of HTTA–Eu³⁺ and HTTA–Tb³⁺ (the HTTA–Eu³⁺/Tb³⁺ mixture) to be used as a ratiometric luminescence sensor for the time-resolved luminescence detection of pH with the intensity ratio of its Tb³⁺ emission at 540 nm to its Eu³⁺ emission at 610 nm, I_540 nm/I_610 nm, as a signal. Moreover, the UV absorption spectrum changes of the HTTA–Eu³⁺/Tb³⁺ mixture at different pHs (pH 4.0–7.0) also display a ratiometric response to the pH changes with the ratio of absorbance at 290 nm to that at 325 nm, A_290 nm/A_325 nm, as a signal. This feature enables the HTTA–Eu³⁺/Tb³⁺ mixture to have an additional function for the pH detection with the absorption spectrometry technique. For loading the complexes into the living cells, the acetoxymethyl ester of HTTA was synthesized and used for loading HTTA–Eu³⁺ and HTTA–Tb³⁺ into the cultured HeLa cells. The luminescence imaging results demonstrated the practical utility of the new sensor for the time-resolved luminescence cell imaging application.     

Magneto-structural study on a series of rhenium(IV) complexes containing biimH2, pyim and bipy ligands

Three rhenium(IV) mononuclear compounds of formulae [ReCl₄(biimH₂)] · 2DMF (1), [ReCl₄(pyim)] · DMF (2) and [ReCl₄(bipy)] (3) (biimH₂ = 2,2′-biimidazole, pyim = 2-(2′-pyridyl)imidazole, bipy = 2,2′-bipyridine and DMF = N,N-dimethylformamide) have been prepared and characterized. The crystal structure of 2 was determined by single crystal X-ray diffraction. Compound 2 crystallizes in the monoclinic system with P2₁/c as space group. The rhenium atom is six-coordinated by four Cl atoms and two nitrogen atoms from a bidentate pyim ligand [average values of Re–Cl and Re–N bonds lengths being 2.330(2) and 2.117(4) Å, respectively]. The magnetic properties were investigated from susceptibility measurements performed on polycrystalline samples of 1–3 in the temperature range 1.9–300 K. The magnetic behaviour found is typical of antiferromagnetically coupled systems, and they exhibit susceptibility maxima at 2.8 (1 and 2) and 5.6 K (3). Short Re^IV–Cl?Cl–Re^IV contacts through space account for the antiferromagnetic behaviour observed.     

Synthesis,crystal structures and spectroscopic studies of praseodymium(III) malonate complexes

Reactions of malonic acid (H₂mal) with PrCl₃·6H₂O afforded the known complex [Pr₂(mal)₃(H₂O)₆]_n (1), and compounds [Pr₂(mal)₃(H₂O)₆]_n·2nH₂O (2·2nH₂O), [PrCl(mal)(H₂O)₃]_n·0.5nH₂O (3·0.5nH₂O) and [Pr(mal)(Hmal)(H₂O)₃]_n·nH₂O (4·nH₂O) using various reaction ratios, reaction media (H₂O, MeOH) and pH values. Analogous reactions with CeCl₃·7H₂O afforded compounds [Ce₂(mal)₃(H₂O)₆]_n (5), [CeCl(mal)(H₂O)₃]_n·nH₂O (6·nH₂O) and [Ce(mal)(Hmal)(H₂O)₃]_n·nH₂O (7·nH₂O). Compounds 2·2nH₂O and 3·0.5nH₂O were characterized by X-ray crystallography, and 4–7 by microanalytical and spectroscopic data. The malonate(-2) ligand adopts three different coordination modes in the structures of 1–3, i.e., the μ₂-κO:κO′:κO″ and the μ₄-κ²O:κO′:κ²O″:κO? in 1 and 2 leading to a 3D network structure, and the μ₃-κ²O:κO′:κ²O″:κO? in 3 promoting an 1D structure. The thermal decomposition of 1 and 3·0.5nH₂O was monitored by TG/DTA and TG/DTG measurements. The structural features of 1–3 are discussed in terms of known malonato(-2) Ln^III and Ca^II complexes. The bioinorganic chemistry relevance of our results is discussed.     

Electrochemical assessment of water|ionic liquid biphasic systems towards cesium extraction from nuclear waste

A room temperature ionic liquid (IL) composed of a quaternary alkylphosphonium (trihexyltetradecylphosphonium, P₆₆₆₁₄⁺) and tetrakis(pentafluorophenyl)borate anion (TB⁻) was employed within a water|P₆₆₆₁₄TB (w|P₆₆₆₁₄TB or w|IL) biphasic system to evaluate cesium ion extraction in comparison to that with a traditional water|organic solvent (w|o) combination. ¹³⁷Cs is a major contributor to the radioactivity of spent nuclear fuel as it leaves the reactor, and its extraction efficiency is therefore of considerable importance. The extraction was facilitated by the ligand octyl(phenyl)-N,N′-diisobutylcarbamoylphosphine oxide (CMPO) used in TRans-Uranium EXtraction processes and investigated through well established liquid|liquid electrochemistry. This study gave access to the metal ion to ligand (1:n) stoichiometry and overall complexation constant, β, of the interfacial complexation reaction which were determined to be 1:3 and 1.6 × 10¹¹ at the w|P₆₆₆₁₄TB interface while the study at w|o elicited an n equal to 1 with β equal to 86.5. Through a straightforward relationship, these complexation constant values were converted to distribution coefficients, δ_α, with the ligand concentrations studied for comparison to other studies present in the literature; the w|o and w|IL systems gave δ_α of 2 and 8.2 × 10⁷, respectively, indicating a higher overall extraction efficiency for the latter. For the w|o system, the metal ion-ligand stoichiometries were confirmed through isotopic distribution analysis of mass spectra obtained by the direct injection of an emulsified water–organic solvent mixture into an electron spray ionization mass spectrometer.     

Chiral cyclopentadienyl ruthenium(II) complexes with P,P-ligands derived from (1R,2R)-1,2-diaminocyclohexane: Synthesis,crystal structures and catalytic activity in Diels–Alder reactions

Chiral cyclopentadienyl ruthenium(II) complexes [CpRu(L1–L3)Cl] (5–7) have been prepared by reaction of [CpRu(PPh₃)₂Cl] with chiral P,P-ligands (1R,2R)-1,2-bis(diphenylphosphinamino)cyclohexane (L1), N,N′-[bis-(3,3′-bis-tert-butyl-5,5′-bis-methoxy-1,1′-biphenyl-2,2′-diyl)phosphite]-(1R,2R)-1,2-diaminocyclohexane (L2) and N,N′-[bis-(R)-1,1′-binaphtyl-2,2′-diyl)phosphite]-(1R,2R)-1,2-diaminocyclohexane (L3). The molecular structures of 5 and 6 have been determined by single-crystal X-ray analysis. Studies on catalytic activity of the cations derived from (5–7) by treatment with AgSbF₆, are also reported.     

Highly electrochemiluminescent Ru(II) complexes containing 1,3-dihydro-1,1,3,3-tetramethyl-7,8-diazacyclopenta[1]phenanthren-2-one ligand

A series of new ruthenium(II) complexes containing 1,3-dihydro-1,1,3,3-tetramethyl-7,8-diazacyclopenta[1]phenanthren-2-one (DTDP) ligand, such as [Ru(DTDP)_n(L)_3−n]²⁺ (L = 2,2′-bipyridyl (bpy), 4,4′-dimethyl-2,2′-bipyridyl (dmbpy), o-phenanthroline (o-phen), 5-chloro-o-phenanthroline (o-phen-Cl), 2,2′-bipyridine-4,4′-dicarboxaldehyde (bpy-(CHO)₂), n = 1, 2, 3) were synthesized and examined as ECL materials. All the complexes were characterized in terms of electrochemical redox potential and relative ECL intensity, and were compared to the well-known tris(o-phenanthroline) ruthenium(II) complex. Most of the synthesized Ru(II) complexes containing the DTDP ligand exhibited more intense ECL emissions than [Ru(o-phen)₃]²⁺. In particular, the ECL intensities of [Ru(DTDP)(o-phen)₂]²⁺ and [Ru(DTDP)(bpy-(CHO)₂)₂]²⁺ were observed to be as high as 9-fold and 20-fold greater, respectively, than the ECL intensity of [Ru(o-phen)₃]²⁺.     

Synthesis and reactions of heterodinuclear organopalladium complex having an unsymmetrical PN ligand

Novel heterodinuclear organopalladium complexes having an unsymmetrical PN ligand (Et₂NC₂H₄PPh₂-κ²N,P)RPd-ML_n (ML_n = Co(CO)₄; R = Me (2a), Ph (2b), ML_n = MoCp(CO)₃; R = Ph (3b)) are synthesized by metathetical reactions of PdRX(Et₂NC₂H₄PPh₂-κ²N,P) (X = I, NO₃) with Na⁺[ML_n]⁻. Reversible dissociation of the Pd-N bond in 3b is revealed by variable temperature NMR studies. Reactions of 2a and 2b with CO yield corresponding acyl complexes (Et₂NC₂H₄PPh₂-κ²N,P)(RCO)Pd-Co(CO)₄ (R = Me (5a), Ph (5b)). Rate of CO insertion for 2a and 2b is significantly faster than those for mononuclear methylpalladium complex, PdMeI(Et₂NC₂H₄PPh₂-κ²N,P) (1a), and methylpalladium-cobalt complex with a 1,2-bis(diphenylphosphino)ethane (dppe) ligand, (dppe-κ²P,P′)MePd-Co(CO)₄ (6a). 5a smoothly reacts with nucleophiles such as diethylamine, methanol and benzenethiol to give corresponding amide, ester and thioester, respectively. These reactions of 5a are also significantly faster than those of corresponding mononuclear analogues and the similar heterodinuclear complexes with symmetrical bidentate ligands such as 1,2-bis(diphenylphosphino)ethane or N,N,N′,N′-tetramethylethylenediamine ligand.