Spin Crossover in a Family of Iron(II) Complexes with Hexadentate ligands: Ligand Strain as a Factor Determining the Transition Temperature

This paper reports the synthesis of a family of mononuclear complexes [Fe(L)]X₂ (X=BF₄, PF₆, ClO₄) with hexadentate ligands L=Hpy-DAPP ({bis[N-(2-pyridylmethyl)-3-aminopropyl](2-pyridylmethyl)amine}), Hpy-EPPA ({[N-(2-pyridylmethyl)-3-aminopropyl][N-(2-pyridylmethyl)-2-aminoethyl](2-pyridylmethyl)amine}) and Hpy-DEPA ({bis[N-(2-pyridylmethyl)-2-aminoethyl](2-pyridylmethyl)amine}). The systematic change of the length of amino-aliphatic chains in these ligands results in chelate rings of different size: two six-membered rings for Hpy-DAPP, one five- and one six-membered rings for Hpy-EPPA, and two five-membered rings for Hpy-DEPA. The X-ray analysis of three low-spin complexes [Fe(L)](BF₄)₂ revealed similarities in their molecular and crystal structures. The magnetic measurements have shown that all synthesized complexes display spin-crossover behavior. The spin-transition temperature increases upon the change from six-membered to five-membered chelate rings, clearly demonstrating the role of the ligand strain. This effect does not depend on the nature of the counter ion. We discuss the structural features accountable for the strain effect on the spin-transition temperature.     

Reaction of N-(2-pyridylmethyl)-3,5-dimethylbenzamide and N-(3-pyridylmethyl)-3,5-dimethylbenzamide N-oxides with acetic anhydride

As a continuation of our work on the reaction of N-pyridylmethyl-3,5-dimethylbenzamide N-oxides with acetic anhydride, we now report a study of the reaction of N-(2-pyridylmethyl)-3,5-dimethylbenzam.de N-oxide ( 5 ) and N-(3-pyridylmethyl)-3,5-dimethylbenzamide N-oxide ( 6 ) with acetic anhydride. Compound 5 gave N,N′-di(3,5.dimethylbenzoyl)-1,2-di(2.pyridyl)ethenediamine ( 7 ) and 3,5-dimethylbenzamtde ( 8 ). Compound 6 afforded three products formulated as 2-acetoxy-3-(3,5-dimethylbenzoylaminomethyl)pyridine ( 12 ), 3-(3,5-dimethylbenzoylaminomethyl)-2-pyridone ( 13 ) and 5-(3,5-dimethylbenzoylaminomethyl)-2-pyridone ( 14 ). Analytical and spectral data are presented which support the structures proposed.     

Pyridinderivate als Komplexbildner. XI. Die Thermodynamik der Metallkomplexbildung mit Bis-, Tris- und Tetrakis[(2-pyridyl)methyl]-aminen

Pyridine Derivatives as Complexing Agents XI. Thermodynamics of Metal Complex Formation with Bis-, Tris- and Tetrakis[(2-pyridyl)methyl]-amines. The equilibria between H⁺, Mn²⁺, Fe²⁺, Co²⁺, Ni²⁺, Cu²⁺, Cd²⁺, Pb²⁺, Hg²⁺ and Ag⁺, and the ligands bis(2-pyridylmethyl)-amine (=DPA), tris(2-pyridylmethyl)-amine (=TPA), tris(6-methyl-2-pyridylmethyl)-amine (=TLA) and N,N,N′,N′-tetrakis(2-pyridylmethyl)-ethylenediamine (=TPEN) have been studied. Only the stability constants of DPA and TLA with almost all these cations were obtained using the pH method. For the other ligands, the complexes are already formed in acid solutions and only the use of different ligand-ligand or metal-metal exchanges as well as of pM methods were successful. The protonation constants indicate that for DPA the protonation occurs firstly at the aliphatic nitrogen atom whereas in all other cases only the pyridine groups can be protonated. The thermodynamic functions of protonation are in agreement with this interpretation. The stability constants of the complexes are often similar in magnitude to those of the analogous aliphatic amines, in spite of the much lower basicities of the pyridine derivatives. The Fe(II)N₆ species of DPA and TPEN are appreciably more stable than those of the corresponding aliphatic ligands. This is due to the formation of low-spin complexes with an unexpected ΔH value. Comparison of the thermodynamic data of formation of the complexes with TPA and TLA shows the effect of the three bulky methyl groups of the second ligand. As a consequence of steric hindrance and of the major dehydration, ΔH and less ΔS are more positive for M(TLA)²⁺ than for M(TPA)²⁺. Therefore M(TLA)²⁺ is normally much less stable than M(TPA)²⁺. The data for MnTPA²⁺ and ZnTPA²⁺ appear to indicate that in these complexes the coordination number of the metal ion is seven and four respectively. In addition to the complexes ML²⁺, with these two ligands hydroxo complexes ML(OH)⁺ are formed at remarkably low pH. Further TPEN seems to be sexidentate in the 1:1 complexes with Mn²⁺, Co²⁺ and Ni²⁺ but quinquedentate in those with Cu²⁺ and Zn²⁺, also in agreement with the spectra in solution and of the solid complex salts. The reaction: M(DPA)₂²⁺ + TPEN → M(TPEN)²⁺ + 2DPA is for all metal ions favoured by ΔH and ΔS, whereas in the case of the corresponding aliphatic ligands only by the second term. This result is explained in terms of a different magnitude of hydration of the two sexidentate ligands as a consequence of the presence of the hydrophobic aromatic rings in TPEN.     

Interaction between peroxide ion and phenol group which are coordinated to the same iron(III) ion

We have prepared several new iron(III) complexes with ligands which contain a phenol group; these are tetradentate [(X-phpy)H, X and H(phpy) represent the substituents on the phenol ring and N,N-bis(2-pyridylmethyl)-N-(2-hydroxybenzyl)amine, respectively] and pentadentate ligands [(R-enph-X)H; R=ethyl(Et) or methyl(Me) derivative and H(Me-enph) denotes N,N-bis(2-pyridylmethyl)-N″-methyl-N″-(2″-hydroxyl-benzylamine)ethylenediamine] and have determined the crystal structures of Fe(phpy)Cl₂, Fe(5-NO₂-phpy)Cl₂, and Fe(Me-enph)ClPF₆, which are of a mononuclear six-coordinate iron(III) complex with coordination of one or two chloride ion(s). These compounds are highly colored (dark violet) due to the coordination of phenol group to an iron(III) atom. When hydrogen peroxide was added to the solution of the iron(III) complex, a color change occurs with bleaching of the violet color, indicating that oxidative degradation of the phenol moiety occurred in the ligand system. The bleaching of the violet color was also observed by the addition of t-butylhydroperoxide. The rate of the disappearance of the violet color is highly dependent on the substituent on the phenol ring; introduction of an electron-withdrawing group in the phenol ring decreases the rate of bleaching, suggesting that disappearance of the violet band should be due to a chemical reaction between the phenol group and a peroxide adduct of the iron(III) species with an η¹-coordination mode and that in this reaction the peroxide adduct acts as an electrophile towards phenol ring. The intramolecular interaction between the phenol moiety and an iron(III)-peroxide adduct may induce activation of the peroxide ion, and this was supported by several facts that the solution containing an iron(III) complex and hydrogen peroxide exhibits high activities for degradation of nucleosides and albumin.     

New organic picolylamine-type ligands and electrochemical study of their complexation with Cu(MeCN)<Subscript>4</Subscript>ClO<Subscript>4</Subscript>

A series of novel organic ligands with dipicolylamine and disulfide groups connected by polymethylene, alkylaryl, alkoxyaryl, or alkoxycarbonyl linker was synthesized. The electrochemical study by cyclic voltammetry was carried out for two synthesized ligands, and the formation of the complexes with Cu(MeCN)ClO₄ in the solution or on the gold electrode surface was established. The complex of Cu^I with 1,24-bis[N,N-bis(2-pyridylmethyl)-glycinoyloxy]-12,13-dithiatetracosane chemisorbed on the Au electrode is capable of binding molecular oxygen from solution.     

Microwave-assisted synthesis of N,N-bis-(2-pyridylmethyl)amine derivatives. Useful ligands in coordination chemistry

Microwave-assisted synthesis of the ligands N,N-bis-(2-pyridylmethyl)amine (BMPA), N-(methylpropanoate)-N,N-bis-(2-pyridylmethyl)amine (MPBMPA), N-(propanamide)-N,N-bis-(2-pyridylmethyl)amine (PABMPA), PNBMPA (N-(3-propionitrile)-N,N-bis-(2-pyridylmethyl)amine), N-(3-aminopropyl)-N,N-bis-(2-pyridylmethyl)amine (APBMPA), and lithium N-(proponoate)-N,N-bis-(2-pyridylmethyl)amine (LiPBMPA) are reported. High yields and short reaction time were obtained for condensation and Michael addition.     

Complexes of mono- and bis(2-carboxyethyl)-2-picolylamine: Synthesis and crystal and molecular structures

N-(2-Pyridylmethyl)iminodipropionic (I) and N-(2-pyridylmethyl)-3-aminopropionic acids (II) were obtained. A reaction of acid I with a Cu(II) salt gave a 2: 2 complex (III); a reaction of acid II with a Ni(II) salt yielded a 1 : 2 complex (IV). The crystal structures of these complexes were determined by X-ray diffraction. The abilities of compounds I and II to form complexes were compared with the literature data for other ligands containing the N-(2-pyridylmethyl)amino fragment. The structural features of the chelate complexes with 2-aminomethylpyridine derivatives were revealed, depending on the other substituents and the metal center.     

Oxidative Dehydrogenation in Complexes of Transition Metals (Cu(II), Co(II), Ni(II)) with N,N"-Di(2-Hydroxybenzyl)diamines

Potentially tetradentate ligands N,N"-di(2-hydroxybenzyl)ethylenediamine (L¹) and N,N"-di(2-hydroxybenzyl)o-phenylenediamine (L²) and complexes of Cu(II), Co(II), and Ni(II) with L¹and L²were synthesized. The EPR and electronic spectroscopy methods were used to reveal the octahedral structure of the Cu(II) complex with L¹in the solid state. In water–alcohol solutions, the Cu(II) and Ni(II) complexes with both ligands have distorted octahedral structures. The Co(II) complexes form dioxygen adduct with L¹. In the presence of oxygen, the ligands in the obtained complex compounds can undergo oxidative dehydrogenation with selective formation of the respective disalicylaldimines. In the case of L², the oxidative dehydrogenation is observed for the complexes of all studied metals in comparatively mild conditions (T= 30°C, methanol and other solvents), while in the case of L¹, it occurs only with the Co(II) complexes in the presence of pyridine.     

Synthesis and Structural Characterisation of Two Copper(II) Complexes of <Emphasis Type="Italic">N</Emphasis>-(1-acetyl-2-propylidene) (2-pyridylmethyl) amine

Two new complexes [CuBr(C₁₁H₁₃N₂O)] (1) and [Cu(NCO)(C₁₁H₁₃N₂O)] (2) containing the tridentate Schiff base ligand, N-(1-acetyl-2-propylidene)(2-pyridylmethyl) amine which is the 1:1 condensation product of acetylacetone and 2-aminomethylpyridine, have been synthesised and characterised by elemental analysis, IR and electronic spectra, electrochemical study and single crystal X-ray diffraction study. Crystal structures reveal that the copper atom in both the complexes are in square geometry formed by the N₂O donor set of the Schiff base and a bromine atom in 1 and one cyanate ligand in 2. Both bromide and isocyanate ligands act in a terminal monodentate fashion.     

Synthesis,characterization and crystal structure of some new Mn(II) and Zn(II) macroacyclic Schiff base complexes derived from two new asymmetrical (N5) branched amines and pyridine-2-carbaldehyde or O-vaniline and their antibacterial properties

Two new branched pentadentate amines (N₅), 3,6-bis(2-pyridylmethyl)-5 methyl-3,6-diazaheptane diazahexane-1-amine (1) and 4,7-bis(2-pyridylmethyl)-6-methyl-4,7-diazaheptane-1-amine (2) have been prepared. These have been used for the synthesis for the eight new macroacyclic Schiff base complexes, by template [1 + 1] condensation of pyridine-2-carbaldehyde or O-vaniline and amines (1 and 2) in the presence of Mn(II) and Zn(II) metal ions in methanol. The isolated complexes were characterized by a combination of microanalysis, IR and Mass spectroscopy. The structure of MnL¹(ClO₄)₂ indicates that in the solid state the Mn(II) ion adopts a slightly distorted octahedral geometry. The synthesized compounds have antibacterial activity against the three Gram-positive bacteria: Enterococcus faecalis, Bacillus cereus and Staphylococcus epidermidis and also against the three Gram-negative bacteria: Citrobacter freundii, Enterobacter aerogenes and Salmonella typhi. The structure of the complexes derived from pyridine-2-carbaldehyde and metal–ligand interactions in these complexes were also theoretically studied. It was indicated that the structure of complexes is similar to each other and metal–ligand interactions depend mainly on the nature of metal ion and is similar for this series of ligands.     

Dansylated Polyamines as Fluorescent Sensors for Metal Ions: Photophysical Properties and Stability of Copper(II) Complexes in Solution

Protonation and the Cu^II complexation constants of the dansylated polyamines N‐dansylethylenediamine ( 1 ), N‐dansyldiethylenetriamine ( 2 ), N‐dansyltriethylenetetramine ( 3 ), N′‐[2‐(dansylamino)ethyl]diethylenetriamine ( 4 ), and tris(2‐dansylaminoethyl)amine ( 5 ) were determined by glass‐electrode potentiometry in MeOH/H₂O 9 : 1 (v/v) solution. For ligands 3 and 4 , the determinations were also performed in aqueous solution. The complexes formed by these ligands in neutral form correspond to those observed for the analogous unsubstituted monoprotonated amines, whereas, when the ligands are deprotonated at the sulfonamide moiety, the species parallel those of the corresponding amines. The molecular structures of the complexes were deduced from the VIS absorption spectra. The crystal structure of the [CuL₂H₋₂] complex 6 of ligand 1 (L) was determined by X‐ray diffraction. The study of the photophysical properties of the ligands 3 – 5 showed that they are good fluorescent sensors for copper(II), which induced fluorescence quenching. Time‐resolved fluorescence measurements allowed us to clarify the sensing mechanism. The pH dependence of the quenching effect demonstrated that it occurs for all Cu²⁺ complexes, even for species in which the sulfonamide moiety is not deprotonated. Sensing of Cu²⁺ was compared with that of other metal ions (Co²⁺, Ni²⁺, Zn²⁺, Cd²⁺, Hg²⁺), and selectivity was studied as a function of pH. Ligands 3 and 4 were found to be selective chemosensors for Cu²⁺ in weakly acidic solution (pH ca. 4 – 5).     

Complexation of N4-Tetradentate Ligands with Nd(III) and Am(III)

To improve understanding of aza-complexants in trivalent actinide?Clanthanide separations, a series of tetradentate N-donor ligands have been synthesized and their complexation of americium(III) and neodymium(III) investigated by UV?Cvisible spectrophotometry in methanolic solutions. The six pyridine/alkyl amine/imine ligands are N,N??-bis(2-methylpyridyl)-1,2-diaminoethane, N,N??-bis(2-methylpyridyl)-1,3-diaminopropane, trans-N,N-bis(2-pyridylmethyl)-1,2-diaminocyclohexane (BPMDAC), N,N??-bis(2-pyridylmethyl)piperazine, N,N??-bis-[pyridin-2-ylmethylene]ethane-1,2-diamine, and trans-N,N-bis-([pyridin-2-ylmethylene]-cyclohexane-1,2-diamine. Each ligand has two pyridine groups and two aliphatic amine/imine N-donor atoms arranged with different degrees of preorganization and structural backbone rigidity. Conditional stability constants for the complexes of Am(III) and Nd(III) by these ligands establish the selectivity patterns. The overall selectivity of Am(III) over Nd(III) is similar to that reported for the terdentate bis(dialkyltriazinyl)pyridine molecules. The cyclohexane amine derivative (BPMDAC) is the strongest complexant and shows the highest selectivity for Am(III) over Nd(III) while the imines appear to prefer a bridging arrangement between two cations. These results suggest that this series of ligands could be employed to develop an enhanced actinide(III)?Clanthanide(III) separation system.     

Structural characterisation of mononuclear zinc(ii) complexes of 4-methyl-3,5-di(2-pyridyl)-4H-1,2,4-triazole with three-atom co-ligands: [ZnII(medpt)2X]ClO4 (X?=?NCS?, N3?, NO2?)

The reaction of 4-methyl-3,5-di(2-pyridyl)-4H-1,2,4-triazole (medpt) with Zn(ClO₄)₂·6H₂O and NaSCN, NaN₃ or NaNO₂ in a 2:1:1 molar ratio in MeOH/H₂O (9:1) affords the mononuclear complexes [Zn^II(medpt)₂(NCS)]ClO₄, [Zn^II(medpt)₂(N₃)]ClO₄ and [Zn^II(medpt)₂(NO₂)]ClO₄, respectively. All three complexes have been structurally characterised and found to feature unusual coordination polyhedra for 3,5-di(2-pyridyl)-4H-1,2,4-triazole complexes. In [Zn^II(medpt)₂(NCS)]ClO₄ and [Zn^II(medpt)₂(N₃)]ClO₄, the zinc atom resides within a distorted square-pyramidal N₅ coordination sphere [τ = 0.22 and 0.04, respectively] with two bidentate medpt ligands bound equatorially and the pseudohalide ion coordinating as a unidentate co-ligand in the apical position. In contrast, the NO₂ ⁻ ion in [Zn^II(medpt)₂(NO₂)]ClO₄ acts as a bidentate ligand, which leads to a strongly distorted N₄O₂ coordination environment about the metal centre.     

Coordination modes of two flexidentate salicylaldimine ligands derived from N-(3-aminopropyl)morpholine toward zinc and copper

Two flexidentate Schiff-base ligands condensed from salicylaldehyde or 5-chlorosalicylaldehyde with N-(3-aminopropyl)morpholine were prepared in situ and reacted with Zn(II) and Cu(II) salts. Upon complexation, the Schiff bases underwent deprotonation at hydroxyl to act as mono-anionic ligands. When a ligand?:?metal ratio of 2?:?1 was applied, the deprotonated Schiff bases coordinated metal ions through phenolate and imine in a square-planar or tetrahedral geometry. In contrast, 5-chlorosalicylaldimine reacted with the metal ions in a 1?:?1 ratio to form complexes wherein morpholine nitrogen also participates in an N,N,O-tridentate coordination mode. The structures of the complexes were characterized by spectroscopic methods and single-crystal X-ray diffraction.     

Comparison of Nonheme Manganese- and Iron-Containing Flavone Synthase Mimics

Heme and nonheme-type flavone synthase enzymes, FS I and FS II are responsible for the synthesis of flavones, which play an important role in various biological processes, and have a wide range of biomedicinal properties including antitumor, antimalarial, and antioxidant activities. To get more insight into the mechanism of this curious enzyme reaction, nonheme structural and functional models were carried out by the use of mononuclear iron, [Fe^II(CDA-BPA*)]²⁺ (6) [CDA-BPA = N,N,N’,N’-tetrakis-(2-pyridylmethyl)-cyclohexanediamine], [Fe^II(CDA-BQA*)]²⁺ (5) [CDA-BQA = N,N,N’,N’-tetrakis-(2-quinolilmethyl)-cyclohexanediamine], [Fe^II(Bn-TPEN)(CH₃CN)]²⁺ (3) [Bn-TPEN = N-benzyl-N,N’,N’-tris(2-pyridylmethyl)-1,2-diaminoethane], [Fe^IV(O)(Bn-TPEN)]²⁺ (9), and manganese, [Mn^II(N4Py*)(CH₃CN)]²⁺ (2) [N4Py* = N,N-bis(2-pyridylmethyl)-1,2-di(2-pyridyl)ethylamine)], [Mn^II(Bn-TPEN)(CH₃CN)]²⁺ (4) complexes as catalysts, where the possible reactive intermediates, high-valent Fe^IV(O) and Mn^IV(O) are known and well characterised. The results of the catalytic and stoichiometric reactions showed that the ligand framework and the nature of the metal cofactor significantly influenced the reactivity of the catalyst and its intermediate. Comparing the reactions of [Fe^IV(O)(Bn-TPEN)]²⁺ (9) and [Mn^IV(O)(Bn-TPEN)]²⁺ (10) towards flavanone under the same conditions, a 3.5-fold difference in reaction rate was observed in favor of iron, and this value is three orders of magnitude higher than was observed for the previously published [Fe^IV(O)(N2Py2Q*)]²⁺ [N,N-bis(2-quinolylmethyl)-1,2-di(2-pyridyl)ethylamine] species.     

Synthesis and Characterization of Two vic-Dioximes Containing the 1,3-Dioxolane Ring and 1,4-Diaminobutane and Their Cobalt(II), Nickel(II), Copper(II) and Zinc(II) Metal Complexes

Two new vic-dioxime ligands, (E,E)-N-{4-[(1,4-dioxaspiro[4.4]non-2-ylmethyl)amino]butyl}-N-hydroxy-2-(hydroxyimino)ethanimidamide (L¹H₂) and (E,E)-N-{4-[(1,4-dioxaspiro[4.5]dec-2-ylmethyl)amino]butyl}-N-hydroxy-2-(hydroxyimino)ethanimidamide (L²H₂) containing two different heteroatoms (N,O) have been prepared from anti-chloroglyoxime, N-(1,4-dioxaspiro[4.4]non-2-ylmethyl)butane-1,4-diamine (3) and N-(1,4-dioxaspiro[4.5]dec-2-ylmethyl)butane-1,4-diamine (4). Co^II, Ni^II and Cu^II complexes of the ligands have a metal:ligand ratio of 1:2 and the ligands coordinate through the two N atoms, as do most of the vic-dioximes. However, Zn^II complexes of the ligands have a metal:ligand ratio of 1:1 and the ligands are coordinated only by the N, O atoms of the vic-dioximes. In the Co^II complexes two water molecules, and in the Zn^II complexes a chloride ion and a water molecule, are also coordinated to the metal ion. The structures of the compounds were determined by a combination of elemental analysis, magnetic moments, molar conductances, thermogravimetric analysis (t.g.a.) and spectroscopic (u.v.–vis., i.r., ¹H- and ¹³C-n.m.r.) data.     

A photochromic dinuclear compound: aquatetrakis(μ‐2,3‐diphenylprop‐2‐enoato)bis(2,3‐diphenylprop‐2‐enoato)ethanolbis(1,10‐phenanthroline)dilanthanum(III)

The title dinuclear complex, (aqua‐1κO)tetrakis(μ‐2,3‐diphenylprop‐2‐enoato‐1:2κ²O:O′)bis(2,3‐diphenylprop‐2‐enoato)‐1κO;2κO‐(ethanol‐2κO)bis(1,10‐phenanthroline)‐1κ²N,N′;2κ²N,N′‐dilanthanum(III), [La₂(C₁₅H₁₁O₂)₆(C₁₂H₈N₂)₂(C₂H₅OH)(H₂O)], contains two similar La^III centres with distorted [LaO₆N₂] bicapped triganol–prismatic coordination polyhedra formed by six phenylcinnamate (PCA⁻ or 2,3‐diphenylprop‐2‐enoate) ligands, two 1,10‐phenanthroline (phen) ligands, a coordinating ethanol molecule and a coordinating water molecule. The two metal centres are bridged by four μ‐PCA⁻ ligands, with the remaining two PCA⁻ ligands coordinated in a monodentate fashion. The noncoordinated carboxylate O atoms on the terminal PCA⁻ ligands form O—H...O hydrogen bonds with the coordinated solvent molecules. Each La centre is also coordinated by a bidentate phen ligand. The PCA⁻ ligands all adopt syn–syn orientations, with the two phenyl rings presenting dihedral angles of about 70°. The compound displays photochromic behaviour both in solution and in the solid state.     

A new group of potential antituberculotics: <Emphasis Type="Italic">N</Emphasis>-(2-pyridylmethyl)salicylamides and <Emphasis Type="Italic">N</Emphasis>-(3-pyridylmethyl)salicylamides

As a part of our systematic study of antimycobacterially active derivatives of salicylamides, a series of nineteen derivatives of N-(2-pyridylmethyl)salicylamides and N-(3-pyridylmethyl)salicylamides was synthesised. The compounds exhibited in vitro activity against Mycobacterium tuberculosis and M. avium. Their lipophilicity, R _M, was measured by thin layer chromatography on silica gel impregnated with trioctadecylsilane and the logarithm of the partition coefficient (octanol-water), logP, was calculated. Both the parameters of lipophilicity correlated. The quantitative relationship between the structure and antimycobacterial activity was calculated. Antimycobacterial activity increased with an increase in lipophilicity. The N-(2-pyridylmethyl)salicylamide derivatives were more active than the derivatives of isomeric N-(3-pyridylmethyl)salicylamides. The geometry of compounds was calculated and the calculation was verified by measuring the length of the hydrogen bond between hydroxyl and carbonyl groups on the salicylic moiety.     

Polymerization of methyl methacrylate in the presence of iron(II) complex with tetradentate nitrogen ligands under conditions of atom transfer radical polymerization

Four tetradentate nitrogen ligands, viz. dichloro{[N,N^′-diphenyl-N,N^′-di(quinoline-2-methyl)]-1,2-ethylene diamine} (1), {[N,N^′-dioctyl-N,N^′-di(quinoline-2-methyl)]-1,2-ethylene diamine} (2), {[N,N^′-dibenzyl-N,N^′-di(quinoline-2-methyl)]-1,2-ethylene diamine} (3), and (1R,2R)-(−)-N,N^′-di(quinoline-2-methyl) di-iminocyclohexane (4), were investigated as novel complexing ligands in iron-mediated atom transfer radical polymerization (ATRP) of methyl methacrylate where ethyl-2-bromoisobutyrate was the initiator in o-xylene at 90 °C. With ligands 1 and 2 the experimental molecular weights increased gradually with monomer conversion. High to moderate conversions (87%, 43%) were obtained in relatively short times (90 min for 1 and 30 min for 2), which indicates an efficient catalyst system, but after these times a dramatic increase in viscosity of the polymerization medium led to loss of control. It is noteworthy that polymerization proceeded in a controlled manner with ligand 1, which has two rather bulky substituents on the N-atom. Such bulky ligands did not work for a copper-based system, where they led to excessive terminations or other side reactions. When the bulkiness of the substituents was significantly increased, as in ligand 3, a decrease in polymerization rate and loss of control occurred. Ligand 4 was less efficient than the other ligands, probably because the ethylene bridge was replaced by cyclohexane bridge.     

Structural Diversity in Alkali Metal and Alkali Metal Magnesiate Chemistry of the Bulky 2,6‐Diisopropyl‐N‐(trimethylsilyl)anilino Ligand

Bulky amido ligands are precious in s‐block chemistry, since they can implant complementary strong basic and weak nucleophilic properties within compounds. Recent work has shown the pivotal importance of the base structure with enhancement of basicity and extraordinary regioselectivities possible for cyclic alkali metal magnesiates containing mixed n‐butyl/amido ligand sets. This work advances alkali metal and alkali metal magnesiate chemistry of the bulky arylsilyl amido ligand [N(SiMe₃)(Dipp)]^? (Dipp=2,6‐iPr₂‐C₆H₃). Infinite chain structures of the parent sodium and potassium amides are disclosed, adding to the few known crystallographically characterised unsolvated s‐block metal amides. Solvation by N,N,N′,N′′,N′′‐pentamethyldiethylenetriamine (PMDETA) or N,N,N′,N′‐tetramethylethylenediamine (TMEDA) gives molecular variants of the lithium and sodium amides; whereas for potassium, PMDETA gives a molecular structure, TMEDA affords a novel, hemi‐solvated infinite chain. Crystal structures of the first magnesiate examples of this amide in [MMg{N(SiMe₃)(Dipp)}₂(μ‐nBu)]_∞ (M=Na or K) are also revealed, though these breakdown to their homometallic components in donor solvents as revealed through NMR and DOSY studies.