Structural studies of (prop‐2‐en‐1‐yl)bis[(pyridin‐2‐yl)methylidene]amine hetero‐scorpionate copper complexes

The structures of five compounds consisting of (prop‐2‐en‐1‐yl)bis[(pyridin‐2‐yl)methylidene]amine complexed with copper in both the Cu^I and Cu^II oxidation states are presented, namely chlorido{(prop‐2‐en‐1‐yl)bis[(pyridin‐2‐yl)methylidene]amine‐κ³N,N′,N′′}copper(I) 0.18‐hydrate, [CuCl(C₁₅H₁₇N₃)]·0.18H₂O, (1), catena‐poly[[copper(I)‐μ₂‐(prop‐2‐en‐1‐yl)bis[(pyridin‐2‐yl)methylidene]amine‐κ⁵N,N′,N′′:C²,C³] perchlorate acetonitrile monosolvate], {[Cu(C₁₅H₁₇N₃)]ClO₄·CH₃CN}_n, (2), dichlorido{(prop‐2‐en‐1‐yl)bis[(pyridin‐2‐yl)methylidene]amine‐κ³N,N′,N′′}copper(II) dichloromethane monosolvate, [CuCl₂(C₁₅H₁₇N₃)]·CH₂Cl₂, (3), chlorido{(prop‐2‐en‐1‐yl)bis[(pyridin‐2‐yl)methylidene]amine‐κ³N,N′,N′′}copper(II) perchlorate, [CuCl(C₁₅H₁₇N₃)]ClO₄, (4), and di‐μ‐chlorido‐bis({(prop‐2‐en‐1‐yl)bis[(pyridin‐2‐yl)methylidene]amine‐κ³N,N′,N′′}copper(II)) bis(tetraphenylborate), [Cu₂Cl₂(C₁₅H₁₇N₃)₂][(C₆H₅)₄B]₂, (5). Systematic variation of the anion from a coordinating chloride to a noncoordinating perchlorate for two Cu^I complexes results in either a discrete molecular species, as in (1), or a one‐dimensional chain structure, as in (2). In complex (1), there are two crystallographically independent molecules in the asymmetric unit. Complex (2) consists of the Cu^I atom coordinated by the amine and pyridyl N atoms of one ligand and by the vinyl moiety of another unit related by the crystallographic screw axis, yielding a one‐dimensional chain parallel to the crystallographic b axis. Three complexes with Cu^II show that varying the anion composition from two chlorides, to a chloride and a perchlorate to a chloride and a tetraphenylborate results in discrete molecular species, as in (3) and (4), or a bridged bis‐μ‐chlorido complex, as in (5). Complex (3) shows two strongly bound Cl atoms, while complex (4) has one strongly bound Cl atom and a weaker coordination by one perchlorate O atom. The large noncoordinating tetraphenylborate anion in complex (5) results in the core‐bridged Cu₂Cl₂ moiety.     

Synthesis,structure, EPR,and DFT calculation on dinuclear paddle wheel Cu(II) complexes with bis-chelate rings

A series of diester-dicarboxylic acids, L¹H₂, L²H₂, L³H₂, L⁴H₂, and L⁵H₂ and their dinuclear Cu₂ complexes [Cu(L¹)CH₃CN]₂ (1), [Cu(L²)H₂O]₂ (2), [Cu(L³)CH₃CN]₂ (3), [Cu(L⁴)EtOH]₂ (4), and [Cu(L⁵)CH₃CN]₂ (5), were synthesized. The crystal structures obtained for 1, 2, and 4 and the density functional theory optimized structures for 2, 3, and 5 illustrated the formation of tetracarboxylate “paddle wheel” complexes. The phthalyl and diphenyl head groups and the spacer moieties were appropriately altered and the size of the chelate ring expanded from 15-membered in 1 to 21-membered in 5. The dinuclear units have strong Cu–Cu interaction with EPR spectra exploring spin coupled features.     

Nickel(II) Complexes of Pentadentate N5 Ligands as Catalysts for Alkane Hydroxylation by Using m‐CPBA as Oxidant: A Combined Experimental and Computational Study

A new family of nickel(II) complexes of the type [Ni(L)(CH₃CN)](BPh₄)₂, where L=N‐methyl‐N,N′,N′‐tris(pyrid‐2‐ylmethyl)‐ethylenediamine (L1, 1 ), N‐benzyl‐N,N′,N′‐tris(pyrid‐2‐yl‐methyl)‐ethylenediamine (L2, 2 ), N‐methyl‐N,N′‐bis(pyrid‐2‐ylmethyl)‐N′‐(6‐methyl‐pyrid‐2‐yl‐methyl)‐ethylenediamine (L3, 3 ), N‐methyl‐N,N′‐bis(pyrid‐2‐ylmethyl)‐N′‐(quinolin‐2‐ylmethyl)‐ethylenediamine (L4, 4 ), and N‐methyl‐N,N′‐bis(pyrid‐2‐ylmethyl)‐N′‐imidazole‐2‐ylmethyl)‐ethylenediamine (L5, 5 ), has been isolated and characterized by means of elemental analysis, mass spectrometry, UV/Vis spectroscopy, and electrochemistry. The single‐crystal X‐ray structure of [Ni(L3)(CH₃CN)](BPh₄)₂ reveals that the nickel(II) center is located in a distorted octahedral coordination geometry constituted by all the five nitrogen atoms of the pentadentate ligand and an acetonitrile molecule. In a dichloromethane/acetonitrile solvent mixture, all the complexes show ligand field bands in the visible region characteristic of an octahedral coordination geometry. They exhibit a one‐electron oxidation corresponding to the Ni^II/Ni^III redox couple the potential of which depends upon the ligand donor functionalities. The new complexes catalyze the oxidation of cyclohexane in the presence of m‐CPBA as oxidant up to a turnover number of 530 with good alcohol selectivity (A/K, 7.1–10.6, A=alcohol, K=ketone). Upon replacing the pyridylmethyl arm in [Ni(L1)(CH₃CN)](BPh₄)₂ by the strongly σ‐bonding but weakly π‐bonding imidazolylmethyl arm as in [Ni(L5)(CH₃CN)](BPh₄)₂ or the sterically demanding 6‐methylpyridylmethyl ([Ni(L3)(CH₃CN)](BPh₄)₂ and the quinolylmethyl arms ([Ni(L4)(CH₃CN)](BPh₄)₂, both the catalytic activity and the selectivity decrease. DFT studies performed on cyclohexane oxidation by complexes 1 and 5 demonstrate the two spin‐state reactivity for the high‐spin [(N5)Ni^II?O^.] intermediate (ts1_hs, ts2_doublet), which has a low‐spin state located closely in energy to the high‐spin state. The lower catalytic activity of complex 5 is mainly due to the formation of thermodynamically less accessible m‐CPBA‐coordinated precursor of [Ni^II(L5)(OOCOC₆H₄Cl)]⁺ ( 5 a ). Adamantane is oxidized to 1‐adamantanol, 2‐adamantanol, and 2‐adamantanone (3°/2°, 10.6–11.5), and cumene is selectively oxidized to 2‐phenyl‐2‐propanol. The incorporation of sterically hindering pyridylmethyl and quinolylmethyl donor ligands around the Ni^II leads to a high 3°/2° bond selectivity for adamantane oxidation, which is in contrast to the lower cyclohexane oxidation activities of the complexes.     

Tracking the dissolution–recrystallization structural transformation (DRST) of copper(II) complexes: a combined crystallographic,mass spectrometric and DFT study

Methanol‐ and temperature‐induced dissolution–recrystallization structural transformation (DRST) was observed among two novel Cu^II complexes. This is first time that the combination of X‐ray crystallography, mass spectrometry and density functional theory (DFT) theoretical calculations has been used to describe the fragmentation and recombination of a mononuclear Cu^II complex at 60 °C in methanol to obtain a binuclear copper(II) complex. Combining time‐dependent high‐resolution electrospray mass spectrometry, we propose a possible mechanism for the conversion of bis(8‐methoxyquinoline‐κ²N,O)bis(thiocyanato‐κN)copper(II), [Cu(NCS)₂(C₁₀H₉NO)₂], Cu1 , to di‐μ‐methanolato‐κ⁴O:O‐bis[(8‐methoxyquinoline‐κ²N,O)(thiocyanato‐κN)copper(II)], [Cu₂(CH₃O)₂(NCS)₂(C₁₀H₉NO)₂], Cu2 , viz. [Cu(SCN)₂( L )₂] ( Cu1 ) → [Cu( L )₂] → [Cu( L )]/ L → [Cu₂(CH₃O)₂(NCS)₂( L )₂] ( Cu2 ). We screened the antitumour activities of L (8‐methoxyquinoline), Cu1 and Cu2 and found that the antiproliferative effect of Cu2 on some tumour cells was much greater than that of L and Cu1 .     

Synthesis,crystal structure and catalytic performance of bis (imino)pyridyl nickel complexes

Two new Ni(II) complexes of 2,6-bis[1-(2,6-diethylphenylimino)ethyl]pyridine (L¹), 2,6-bis[1-(4-methylphenylimino)ethyl]pyridine (L² ) have been synthesized and structurally characterized. Complex Ni(L¹)Cl₂?·?CH₃CN (1), exhibits a distorted trigonal bipyramidal geometry, whereas complex Ni(L¹)(CH₃CN)Cl₂ (2), is six-coordinate with a geometry that can best be described as distorted octahedral. The catalytic activities of complexes 1, 2, Ni{2,6-bis[1-(2,6-diisopropyl-phenylimino)ethyl]pyridine} Cl₂?·?CH₃CN (3), and Ni{2,6-bis[1-(2,6-dimethylphenylimino) ethyl]pyridine}Cl₂?·?CH₃CN (4), for ethylene polymerization were studied under activation with MAO.     

Lanthanide(II) Complexes Supported by N,O‐Donor Tripodal Ligands: Synthesis,Structure, and Ligand‐Dependent Redox Behavior

The preparation and characterization of a series of complexes of the Yb and Eu cations in the oxidation state II and III with the tetradentate N,O‐donor tripodal ligands (tris(2‐pyridylmethyl)amine (TPA), BPA^? (HBPA=bis(2‐pyridylmethyl)(2‐hydroxybenzyl)amine), BPPA^? (HBPPA=bis(2‐pyridylmethyl)(3.5‐di‐tert‐butyl‐2‐hydroxybenzyl)amine), and MPA^2? (H₂MPA=(2‐pyridylmethyl)bis(3.5‐di‐tert‐butyl‐2‐hydroxybenzyl)amine) is reported. The X‐ray crystal structures of the heteroleptic Ln²⁺ complexes [Ln(TPA)I₂] (Ln=Eu, Yb) and [Yb(BPA)I(CH₃CN)]₂, of the Ln²⁺ homoleptic [Ln(TPA)₂]I₂ (Ln=Sm, Eu, Yb) and [Eu(BPA)₂] complexes, and of the Ln³⁺ [Eu(BPPA)₂]OTf and [Yb(MPA)₂K(dme)₂] (dme=dimethoxyethane) complexes have been determined. Cyclic voltammetry studies carried out on the bis‐ligand complexes of Eu³⁺ and Yb³⁺ show that the metal center reduction occurs at significantly lower potentials for the BPA^? ligand as compared with the TPA ligand. This suggests that the more electron‐rich character of the BPA^? ligand results in a higher reducing character of the lanthanide complexes of BPA^? compared with those of TPA. The important differences in the stability and reactivity of the investigated complexes are probably due to the observed difference in redox potential. Preliminary reactivity studies show that whereas the bis‐TPA complexes of Eu²⁺ and Yb²⁺ do not show any reactivity with heteroallenes, the [Eu(BPA)₂] complex reduces CS₂ to afford the first example of a lanthanide trithiocarbonate complex.     

The nature of active species in catalytic systems based on non-heme iron complexes, hydrogen peroxide, and acetic acid for selective olefin epoxidation

The catalytic systems [(BPMEN)Fe^II(CH₃CN)₂](ClO₄)₂/H₂O₂/CH₃OOH and [(TPA)Fe^II(CH₃CN)₂](ClO₄)₂/H₂O₂/CH₃OOH, where BPMEN = N,N′-dimethyl-N,N′-bis(2-pyridylmethyl)-1,2-diaminoethane and TPA = tris(2-pyridylmethyl)amine, provide selective olefin epoxidation. Proton NMR studies showed that the mononuclear iron(IV) oxo complexes [(L)Fe^IV=O]²⁺, with L = BPMEN or TPA, are present in the cited catalytic systems. These intermediates are the decomposition products of the acylperoxo complexes [(L)Fe^III-O₃CCH₃]²⁺. Such a complex was observed by the ²H NMR technique at low temperatures. The [(L)Fe^IV=O]²⁺ and [(L)Fe^V=O]³⁺ oxo complexes are possible active species in the studied catalytic systems.     

Enhancing the Value of Free Metals in the Synthesis of Lanthanoid Formamidinates: Is a Co‐oxidant Needed?

Treatment of N,N′‐bis(aryl)formamidines (ArFormH), N,N′‐bis(2,6‐difluorophenyl)formamidine (DFFormH) or N,N′‐bis(2,6‐diisopropylphenyl)formamidine (DippFormH), with europium metal in CH₃CN is an efficient synthesis of the divalent complexes: [{Eu(DFForm)₂(CH₃CN)₂}₂] ( Eu1 ) or [Eu(DippForm)₂(CH₃CN)₄] ( Eu2 ). The synthetic method was extended to ytterbium, but the metal required activation by addition of Hg⁰. With DFFormH in CH₃CN, [{Yb(DFForm)₂(CH₃CN)}₂] ( Yb1 ) was obtained in good yield, and [Yb(DFForm)₂(thf)₃] ( Yb3 ) was obtained from a synthesis in CH₃CN/THF. Thus, this synthetic method completely circumvents the use of either salt metathesis, or redox transmetallation/protolysis (RTP) protocols to prepare divalent rare‐earth formamidinates. Heating Yb1 in PhMe/C₆D₆ resulted in decomposition to trivalent products, including one from a CH₃CN activation process. For a synthetic comparison, divalent ytterbium DFForm and DippForm complexes were synthesised by RTP reactions between Yb⁰, Hg(R)₂ (R=Ph, C₆F₅), and ArFormH in THF, leading to the isolation of either [Yb(DFForm)₂(thf)₃] ( Yb3 ), or the first five coordinate rare‐earth formamidinate complex [Yb(DippForm)₂(thf)] ( Yb4 b ), and, from adjustment of the stoichiometry, trivalent [Yb(DFForm)₃(thf)] ( Yb6 ). Oxidation of Yb3 with benzophenone (bp), or halogenating agents (TiCl₄(thf)₂, Ph₃CCl, C₂Cl₆) gave [Yb(DFForm)₃(bp)] or [Yb(DFForm)₂Cl(thf)₂], respectively. Furthermore, the structural chemistry of divalent ArForm complexes has been substantially broadened. Not only have the highest and lowest coordination numbers for divalent rare‐earth ArForm complexes been achieved in Eu2 and Yb4 b , respectively, but also dimeric Eu1 and Yb1 have highly unusual ArForm bridging coordination modes, either perpendicular μ‐1κ(N:N′):2κ(N:N′) in Eu1 , or the twisted μ‐1κ(N:N′):2κ(N′:F′) DFForm coordination in Yb1 , both unprecedented in divalent rare‐earth ArForm chemistry and in the wider divalent rare‐earth amidinate field.     

Preparation, crystal structures and oxidation activity of two novel nickel(II) complexes of tripodal ligand containing coordinated solvent molecules

Two novel Ni^II complexes, [Ni(TMPzA)(CH₃CN)(H₂O)]· (ClO₄)₂ (1) and [Ni(TMPzA)(CH₃OH) (NCS)]· (ClO₄) (2), where TMPzA = tris[(3,5-dimethyl-1-pyrazolemethyl)amine], have been synthesized and characterized. Their crystal structures were determined by X-ray diffraction analysis. Both complexes were isolated from the reactions of TMPzA ligand with metal salts, and thiocyanate as the second ligand in CH₃CN solution for (1) and in CH₃OH solution for (2), respectively. The title complexes are mononuclear structures, and which further assembled into a dimer by the intermolecular hydrogen bond in the unit cell, respectively. The solvent molecules participate in coordination. The spectra properties of the two complexes in solution have been further studied and discussed. The oxidation of styrene catalyzed by the title complexes has been studied, and the new complexes show some catalytic activity under the reaction conditions.     

Synthesis,characterization, and X-ray crystal structure analysis of Cd(ΙΙ) and Cu(II) complexes of an acyclic pentadentate Schiff base

Cd(ΙΙ) and Cu(II) complexes of an acyclic pentadentate Schiff base were prepared by template condensation of two equivalents of 2-acetylpyridine with one equivalent of bis(3-aminopropyl)amine in methanol. The resulting complexes [CdL(NO₃)]ClO₄ (1) and [CuL](ClO₄)₂ · CH₃CN (2) were characterized by X-ray crystallography, elemental analysis, IR and mass spectrometry in both cases and by NMR in the case of 1. The X-ray crystallographic structure determination of these complexes revealed six-coordinate distorted octahedral geometry for 1, with the sixth coordination by nitrate and five-coordinate for 2 with trigonal-bipyramidal Cu(II).     

Syntheses and structures of one CuI‐containing coordination polymer and two macrocyclic supramolecular complexes based on flexible 1,3,4‐oxadiazole‐containing ligands

Three coordination complexes with Cu^I centres have been prepared using the symmetrical flexible organic ligands 1,3‐bis{[5‐(quinolin‐2‐yl)‐1,3,4‐oxadiazol‐2‐yl]sulfanyl}propane (L1) and 1,4‐bis{[5‐(quinolin‐2‐yl)‐1,3,4‐oxadiazol‐2‐yl]sulfanyl}butane (L2). Crystallization of L1 with Cu(SO₃CF₃)₂ and of L2 with Cu(BF₄)₂ and Cu(ClO₄)₂ in a CH₂Cl₂/CH₃OH mixed‐solvent system at room temperature afforded the coordination complexes catena‐poly[[copper(I)‐μ‐1,3‐bis{[5‐(quinolin‐2‐yl)‐1,3,4‐oxadiazol‐2‐yl]sulfanyl}propane] methanesulfonate dichloromethane 0.6‐solvate], {[Cu(C₂₅H₁₈N₆O₂S₂)](CF₃SO₃)·0.6CH₂Cl₂}_n, (I), bis(μ‐1,4‐bis{[5‐(quinolin‐2‐yl)‐1,3,4‐oxadiazol‐2‐yl]sulfanyl}butane)dicopper(I) bis(tetrafluoridoborate)–dichloromethane–methanol (1/1.5/1), [Cu₂(C₂₆H₂₀N₆O₂S₂)₂](BF₄)₂·1.5CH₂Cl₂·CH₃OH, (II), and bis(μ‐1,4‐bis{[5‐(quinolin‐2‐yl)‐1,3,4‐oxadiazol‐2‐yl]sulfanyl}butane)dicopper(I) bis(perchlorate)–dichloromethane–methanol (1/2/1), [Cu₂(C₂₆H₂₀N₆O₂S₂)₂](ClO₄)₂·2CH₂Cl₂·CH₃OH, (III). Under the control of the dumbbell‐shaped CF₃SO₃⁻ anion, complex (I) forms a one‐dimensional chain and neighbouring chains form a spiral double chain. Under the control of the regular tetrahedron‐shaped BF₄⁻ and ClO₄⁻ anions, complexes (II) and (III) have been obtained as bimetallic rings, which further interact viaπ–π interactions to form two‐dimensional networks. The anions play a decisive role in determining the arrangement of these discrete molecular complexes in the solid state.     

The reduction of Ag(I) by α‐silylamines R2NCH2SiX3

The introduction of the organosilicon substituent into the α‐position of an amino group results in cardinal change of the amine reactivity irrespective of the coordination state of silicon. Amines R₂NCH₂SiX₃ [R = Me, Et, PhCH₂, CH₂SiX₃; SiX₃ = SiMe₃, Si(OEt)₃, Si(OCH₂CH₂)₃N] easily react with AgNO₃, to give the corresponding ammonium salts (R₂NH⁺ CH₂SiX₃)·NO₃^?. At the same time, Ag(I) is reduced to Ag(0). The interaction of N‐methyl‐N,N‐bis(silatranylmethyl)amine with AgNO₃ has been investigated by EPR spectroscopy. It was proven that the reaction involved a single electron transfer stage with the formation of cation radical of this amine. A mechanism of the reaction is proposed. Copyright © 2006 John Wiley & Sons, Ltd.     

New Functional Cyclic Aminomethylphosphine Ligands for the Construction of Catalysts for Electrochemical Hydrogen Transformations

Eight‐membered cyclic functional bisphosphines, namely 1,5‐di‐aryl‐3,7‐di(2‐pyridyl)‐1,5‐diaza‐3,7‐diphosphacyclooctanes (aryl=2‐pyridyl, m‐tolyl, p‐tolyl, diphenylmethyl, benzyl, (R)‐(+)‐(α‐methyl)benzyl), with 2‐pyridyl substituents on the phosphorus atoms have been synthesized by condensation of 2‐pyridylphosphine, formaldehyde, and the corresponding primary amine. The structures of some of these bisphosphines have been investigated by X‐ray crystallography. The bisphosphines readily form neutral P,P‐chelate complexes [(κ²‐P,P‐L)MCl₂], cationic bis‐P,P‐chelate complexes [(κ²‐P,P‐L)₂M]²⁺, or a five‐coordinate complex [(κ²‐P,P‐L)₂NiBr]Br. The electrochemical behavior of two of the nickel complexes, and their catalytic activities in electrochemical hydrogen evolution and hydrogen oxidation, including the fuel‐cell test, have been studied.     

Copper(II), Cobalt(II), and Nickel(II) Complexes of two Novel Pyridine‐derived Macrocyclic Ligands bearing o‐ and pNitrobenzyl Pendant Groups

The pendant‐armed ligands L¹ and L² were synthesized by N‐alkylation of the four secondary amine groups of the macrocyclic precursor L using o‐nitrobenzylbromide (L¹) and p‐nitrobenzylbromide (L²). Nitrates and perchlorates of Cu^II, Ni^II and Co^II were used to synthesize the metal complexes of both ligands and the complexes were characterized by microanalysis, MS‐FAB, conductivity measurements, IR and UV‐Vis spectroscopy and magnetic studies. The crystal structures of L¹, [CuL¹](ClO₄)₂·CH₃CN·H₂O, [CuL²](ClO₄)₂·6CH₃CN, [CuL²][Cu(NO₃)₄]·5CH₃CN·0.5CH₃OH and [NiL²](ClO₄)₂·3CH₃CN·H₂O were determined by single crystal X‐ray crystallography. These structural analysis reveal the free ligand L¹, three mononuclear endomacrocyclic complexes {[CuL¹](ClO₄)₂·CH₃CN·H₂O, [CuL²](ClO₄)₂·6CH₃CN and [NiL²](ClO₄)₂·3CH₃CN·H₂O} and one binuclear complex {[CuL²][Cu(NO₃)₄]·5CH₃CN·0.5CH₃OH} in which one of the metals is in the macrocyclic framework and the other metal is outside the ligand cavity and coordinated to four nitrate ions.     

Dinuclear cobalt(II) complexes with double phosphate ester bridges and tetradentate ligands having anisole or quinoline appendages

Phosphate esters provide a rigid and stable polymeric backbone in nucleic acids. Metal complexes with phosphate ester groups have been synthesized as structural and spectroscopic models of phosphate‐containing enzymes. Dinucleating ligands are used extensively to synthesize model complexes since they provide the support required to stabilize such complexes. The crystal structures of two dinuclear Co^II complexes, namely bis(μ‐diphenyl phosphato‐κ²O :O ′)bis({2‐methoxy‐N ,N‐bis[(pyridin‐2‐yl)methyl]aniline‐κ⁴N ,N ′,N ′′,O }cobalt(II)) bis(perchlorate), [Co(C₁₂H₁₀O₄P)₂(C₁₉H₁₉N₃O)₂](ClO₄)₂, and bis(μ‐diphenyl phosphato‐κ²O :O ′)bis({N ,N‐bis[(pyridin‐2‐yl)methyl]quinolin‐8‐amine‐κ⁴N ,N ′,N ′′,O }cobalt(II)) bis(perchlorate), [Co(C₁₂H₁₀O₄P)₂(C₂₁H₁₈N₄)₂](ClO₄)₂, with tetradentate 2‐methoxy‐N ,N‐bis[(pyridin‐2‐yl)methyl]aniline (L ¹) and N ,N‐bis[(pyridin‐2‐yl)methyl]quinolin‐8‐amine (L ²) ligands are reported. The complexes have similar structures, with distorted octahedral geometries around the metal centres. Both are centrosymmetric (Z ′ = 0.5), with the Co^II centres doubly bridged by diphenyl phosphate ester groups. A number of aromatic–aromatic interactions are present and differ between the two complexes as the anisole group in L ¹ is replaced by a quinoline group in L ². A detailed study of these interactions is presented.     

Copper(II) complexes with derivatives of salen and tetrahydrosalen: a spectroscopic, electrochemical and structural study

Salen type complexes, CuL, the corresponding tetrahydrosalen type complexes, Cu[H₄]L, and N,N′-dimethylated tetrahydrosalen type complexes, Cu[H₂Me₂]L, were investigated using cyclic voltammetry, and electronic and ESR spectroscopy. In addition, the analogous copper(II) complexes with a derivative of the tetradentate ligand ‘salphen’ [salphen=H₂salphen=N,N′-disalicylidene-1,2-diaminobenzene] were studied. Solutions of CuL, Cu[H₄]L and Cu[H₂Me₂]L are air-stable at ambient temperature, except for the complex Cu(^tBu, Me)[H₄]salphen [H₂(^tBu, Me)[H₄]salphen=N,N′-bis(2-hydroxy-3-tert-butyl-5-methylbenzyl)-1,2-diaminobenzene]. Cu(^tBu, Me)[H₄]salphen interacts with dioxygen and the ligand is oxidatively dehydrogenated (–CH₂–NH–→–C=N–) to form Cu(^tBu, Me)[H₂]salphen and finally, in the presence of base, Cu(^tBu, Me)salphen. X-ray structure analysis of Cu(^tBu, Me)[H₂Me₂]salen confirms a slightly tetrahedrally distorted planar geometry of the CuN₂O₂ coordination core. The complexes were subjected to spectrophotometric titration with pyridine, to determine the equilibrium constants for adduct formation. It was found that the metal center in the complexes studied is only of weak Lewis acidity. In dichlormethane, the oxidation Cu(II)/Cu(III) is quasireversible for the CuL type complexes, but irreversible for the Cu[H₄]L and Cu[H₂Me₂]L type. A poorly defined wave was observed for the irreversible reduction Cu(II)/Cu(I) at potentials less than −1.0 V. The ESR spectra of CuL at both 77 K and room temperature reveal that very well resolved lines can be attributed to the interaction of an unpaired electron spin with the copper nuclear spin, ¹⁴N donor nuclei and to a distant interaction with two equivalent protons [A^Cu(iso)≈253 MHz, A^N(iso)≈43 MHz, A^N(iso)≈20 MHz]. These protons are attached to the carbon atoms adjacent to the ¹⁴N nuclei. In contrast to CuL, the number of lines in the spectra of the complexes Cu[H₄]L and Cu[H₂Me₂]L is greatly reduced. At room temperature, only a quintet with a considerably smaller nitrogen shf splitting constant [A^N(iso)≈27 MHz] is observed. Both factors, planarity and conjugation, are thus essential for the observation of distant hydrogen shf splitting in CuL. Due to the C=N bond hydrogenation, the coordination polyhedra of the complexes Cu[H₄]L and Cu[H₂Me₂]L is more flexible and more sensitive to ligand modification than that of CuL. The electron-withdrawing effect of the phenyl ring of the phenylenediamine bridge is reflected in a reduction of the copper hyperfine coupling constants in Cu(^tBu, Me)[H₄]salphen and Cu(^tBu, Me)[H₂Me₂]salphen complexes [A^Cu(iso)≈215 MHz].     

Syntheses and structures of three macrocyclic supramolecular complexes and one ZnII‐containing coordination polymer generated from a semi‐rigid multidentate N‐containing ligand

Semirigid organic ligands can adopt different conformations to construct coordination polymers with more diverse structures when compared to those constructed from rigid ligands. A new asymmetric semirigid organic ligand, 4‐{2‐[(pyridin‐3‐yl)methyl]‐2H‐tetrazol‐5‐yl}pyridine ( L ), has been prepared and used to synthesize three bimetallic macrocyclic complexes and one coordination polymer, namely, bis(μ‐4‐{2‐[(pyridin‐3‐yl)methyl]‐2H‐tetrazol‐5‐yl}pyridine)bis[dichloridozinc(II)] dichloromethane disolvate, [Zn₂Cl₄(C₁₂H₁₀N₆)₂]·2CH₂Cl₂, ( I ), the analogous chloroform monosolvate, [Zn₂Cl₄(C₁₂H₁₀N₆)₂]·CHCl₃, ( II ), bis(μ‐4‐{2‐[(pyridin‐3‐yl)methyl]‐2H‐tetrazol‐5‐yl}pyridine)bis[diiodidozinc(II)] dichloromethane disolvate, [Zn₂I₄(C₁₂H₁₀N₆)₂]·2CH₂Cl₂, ( III ), and catena‐poly[[[diiodidozinc(II)]‐μ‐4‐{2‐[(pyridin‐3‐yl)methyl]‐2H‐tetrazol‐5‐yl}pyridine] chloroform monosolvate], {[ZnI₂(C₁₂H₁₀N₆)]·CHCl₃}_n, ( IV ), by solution reaction with ZnX₂ (X = Cl and I) in a CH₂Cl₂/CH₃OH or CHCl₃/CH₃OH mixed solvent system at room temperature. Complex ( I ) is isomorphic with complex ( III ) and has a bimetallic ring possessing similar coordination environments for both of the Zn^II cations. Although complex ( II ) also contains a bimetallic ring, the two Zn^II cations have different coordination environments. Under the influence of the I^? anion and guest CHCl₃ molecule, complex ( IV ) displays a significantly different structure with respect to complexes ( I )–( III ). C—H…Cl and C—H…N hydrogen bonds, and π–π stacking or C—Cl…π interactions exist in complexes ( I )–( IV ), and these weak interactions play an important role in the three‐dimensional structures of ( I )–( IV ) in the solid state. In addition, the fluorescence properties of L and complexes ( I )–( IV ) were investigated.     

Synthesis of new mixed ligand complexes of copper(II) dithiocarbamates

New mixed ligand complexes of copper(II) dithiocarbamates of the general formula, [CuCl(R₂dtc)L] or [CuCi(R′ dtc)L] (RCH₃ or C₂H₅, R′ = (CH₂)₅, dtc =-NCSS^? and L = Pyridine, 3-picoline or 4-picoline), have been prepared by the reaction of bis(dithiocarbamato)di-μ-chloro-dicopper(II) complexes with pyridine or picolines. The complexes are found to be non-electrolytes in nitrobenzene. Magnetic susceptibilities, i.r. and electronic spectra of the complexes are reported. A psuedo-tetrahedral structure is suggested for these complexes.     

Effect of Chelate Ring Size in Iron(II) Isothiocyanato Complexes with Tetradentate Tripyridyl‐alkylamine Ligands on Spin Crossover Properties

Iron(II) complexes of the type [Fe(L)(NCS)₂] with tetradentate ligands L are well known to show spin crossover properties. However, this behavior is quite sensitive in regard to small changes of the ligand system. Starting from the thoroughly investigated complex [Fe(tmpa)(NCS)₂] [tmpa = tris(2‐pyridylmethyl)amine, also abbreviated as tpa in the literature] we modified the ligand by increasing systematically the chelate ring sizes from 5 to 6 thus obtaining complexes [Fe(pmea)(NCS)₂], [Fe(pmap)(NCS)₂], and [Fe(tepa)(NCS)₂] [pmea = N,N‐bis[(2‐pyridyl)methyl]‐2‐(2‐pyridyl)ethylamine, pmap = N,N‐bis[2‐(2‐pyridyl)ethyl]‐(2‐pyridyl)methylamine, and tepa = tris[2‐(2‐pyridyl)ethyl]amine]. All complexes were structurally characterized and spin crossover properties were investigated using Mößbauer spectroscopy, magnetic measurements, and IR/Raman analyses. The results demonstrated that only the iron complexes with tmpa and pmea showed spin crossover properties, whereas the complexes with the ligands pmap and tepa only formed high spin complexes. Furthermore, DFT calculations supported these findings demonstrating again the strong influence of ligand environment. Herein the effect of increasing the chelate ring sizes in iron(II) isothiocyanato complexes with tetradentate tripyridyl‐alkylamine ligands is clearly demonstrated.     

Syntheses,Crystal Structures,and Antibacterial Activities of Four Schiff Base Complexes of Copper and Zinc

Four Schiff base complexes, [Cu₂(L1)₂(μ‐NCS)₂] ( 1 ), [Cu₂(L2)₂(μ‐N₃)₂] ( 2 ), Cu[Cu(CH₃COO)(L3)]₂ ( 3 ), and [Zn{Zn(C₃H₄N₂)(L3)}₂(NO₃)](NO₃) ( 4 ) (where L1 = 2‐[(pyridin‐2‐ylmethylimino)methyl]phenol, L2 = 1‐[(pyridin‐2‐ylmethylimino)methyl]naphthalen‐2‐ol, and L3 = bis(salicylidene)‐1, 3‐propanediamine), were synthesized and characterized by elemental analyses, infrared spectroscopy, and single crystal X‐ray determinations. Both 1 and 2 are structurally similar di‐nuclear complexes, which are located at crystallographic inversion centers (with the center of the central Cu₂N₂ ring). In 1 , each copper atom has a slightly distorted square pyramidal configuration, coordinated by two nitrogen atoms and one oxygen atom from L1 and another two terminal nitrogen atoms from two bridging thiocyanate anions. The Cu···Cu separation is 3.466(3) Å. The structure of 2 is similar to that of 1 , with Cu···Cu separation of 3.368(2) Å. Both 3 and 4 are linear tri‐nuclear complexes. In 3 , the central Cu²⁺ ion is located on an inversion centre and has a distorted octahedral coordination involving four bridging O atoms from two Schiff base ligands (L3) in the equatorial plane and one O atom from each bridging acetate group in the axial positions. The coordination around the terminal Cu²⁺ ions is irregular‐square pyramidal, with two O and two N atoms of L3 in the basal plane and one O atom from an acetate group in the apical position. The acetate bridges linking the central and terminal Cu²⁺ ions are mutually trans. The Cu···Cu separation is 3.009(3) Å. In 4 , the coordination configuration of the central and the terminal zinc atoms are similar to that of the 3 , with Zn···Zn separation of 3.153(4) Å. The three Schiff bases and the corresponding three copper complexes exhibit good antibacterial properties, while the zinc complex 4 has nearly no.