Self-assembled metallo-macrocycle based coordination polymers with unsymmetrical amide ligands

A series of metallo-macrocyclic based coordination polymers has been prepared from flexible amide ligands N-6-[(3-pyridylmethylamino)carbonyl]-pyridine-2-carboxylic acid (L1-CH(3)) and N-6-[(4-pyridylmethylamino)carbonyl]-pyridine-2-carboxylic acid (L2-CH(3)). In all but one case, self-assembled dinuclear metallo-macrocyclic units form the basis of the polymeric structures, whereby discrete metal centres, and dinuclear or trinuclear clusters, are linked by the self-assembled macrocycles to give 1D and 2D coordination polymers. In one instance, a 1D coordination polymer is formed in a reaction carried out under ambient conditions; when the same reaction is conducted under solvothermal conditions a 2D structure is formed. In all but two of these structures, the polymeric chains and nets are close-packed within the crystals. In the case of a 6,3-connected 2D coordination polymer {[Cd(3)(L2-CH(3))(3)(NO(3))(L2)(CH(3)OH)](NO(3))(2)·12?H(2)O}(n) (9), small oval channels percolate down the a-axis of the unit cell.     

Reaction behaviour of dinuclear copper(I) complexes with m-xylyl-based ligands towards dioxygen

Intramolecular ligand hydroxylation was observed during the reactions of dioxygen with the dicopper(I) complexes of the ligands L(1)(L(1)=alpha,alpha'-bis[(2-pyridylethyl)amino]-m-xylene) and L(3)(L(3)=alpha, alpha'-bis[N-(2-pyridylethyl)-N-(2-pyridylmethyl)amino]-m-xylene). The dinuclear copper(I) complex [Cu(2)L(3)](ClO(4))(2) and the dicopper(II) complex [Cu(2)(L(1)-O)(OH)(ClO(4))]ClO(4) were characterized by single-crystal X-ray structure analysis. Furthermore, phenolate-bridged complexes were synthesized with the ligand L(2)-OH (structurally characterized [Cu(2)(L(2)-O)Cl(3)] with L(2)=alpha, alpha'-bis[N-methyl-N-(2-pyridylethyl)amino]-m-xylene; synthesized from the reaction between [Cu(2)(L(2)-O)(OH)](ClO(4))(2) and Cl(-)) and Me-L(3)-OH: [Cu(2)(Me-L(3)-O)(mu-X)](ClO(4))(2)xnH(2)O (Me-L(3)-OH = 2,6-bis[N-(2-pyridylethyl)-N-(2-pyridylmethyl)amino]-4-methylphenol and X = C(3)H(3)N(2)(-)(prz), MeCO(2)(-) and N(3)(-)). The magnetochemical characteristics of compounds were determined by temperature-dependent magnetic studies, revealing their antiferromagnetic behaviour [-2J(in cm(-1)) values: -92, -86 and -88; -374].     

First row divalent transition metal complexes of aryl-appended tris((pyridyl)methyl)amine ligands: syntheses, structures, electrochemistry, and hydroxamate binding properties

Divalent manganese, cobalt, nickel, and zinc complexes of 6-Ph(2)TPA (N,N-bis((6-phenyl-2-pyridyl)methyl)-N-((2-pyridyl)methyl)amine; [(6-Ph(2)TPA)Mn(CH(3)OH)(3)](ClO(4))(2) (1), [(6-Ph(2)TPA)Co(CH(3)CN)](ClO(4))(2) (2), [(6-Ph(2)TPA)Ni(CH(3)CN)(CH(3)OH)](ClO(4))(2) (3), [(6-Ph(2)TPA)Zn(CH(3)CN)](ClO(4))(2) (4)) and 6-(Me(2)Ph)(2)TPA (N,N-bis((6-(3,5-dimethyl)phenyl-2-pyridyl)methyl)-N-((2-pyridyl)methyl)amine; [(6-(Me(2)Ph)(2)TPA)Ni(CH(3)CN)(2)](ClO(4))(2) (5) and [(6-(Me(2)Ph)(2)TPA)Zn(CH(3)CN)](ClO(4))(2) (6)) have been prepared and characterized. X-ray crystallographic characterization of 1A.CH(3)()OH and 1B.2CH(3)()OH (differing solvates of 1), 2.2CH(3)()CN, 3.CH(3)()OH, 4.2CH(3)()CN, and 6.2.5CH(3)()CN revealed mononuclear cations with one to three coordinated solvent molecules. In 1A.CH(3)()OH and 1B.2CH(3)()OH, one phenyl-substituted pyridyl arm is not coordinated and forms a secondary hydrogen-bonding interaction with a manganese bound methanol molecule. In 2.2CH(3)()CN, 3.CH(3)()OH, 4.2CH(3)()CN, and 6.2.5CH(3)()CN, all pyridyl donors of the 6-Ph(2)TPA and 6-(Me(2)Ph)(2)TPA ligands are coordinated to the divalent metal center. In the cobalt, nickel, and zinc derivatives, CH/pi interactions are found between a bound acetonitrile molecule and the aryl appendages of the 6-Ph(2)TPA and 6-(Me(2)Ph)(2)TPA ligands. (1)H NMR spectra of 4 and 6 in CD(3)NO(2) solution indicate the presence of CH/pi interactions, as an upfield-shifted methyl resonance for a bound acetonitrile molecule is present. Examination of the cyclic voltammetry of 1-3 and 5 revealed no oxidative (M(II)/M(III)) couples. Admixture of equimolar amounts of 6-Ph(2)TPA, M(ClO(4))(2).6H(2)O, and Me(4)NOH.5H(2)O, followed by the addition of an equimolar amount of acetohydroxamic acid, yielded the acetohydroxamate complexes [((6-Ph(2)TPA)Mn)(2)(micro-ONHC(O)CH(3))(2)](ClO(4))(2) (8), [(6-Ph(2)TPA)Co(ONHC(O)CH(3))](ClO(4))(2) (9), [(6-Ph(2)TPA)Ni(ONHC(O)CH(3))](ClO(4))(2) (10), and [(6-Ph(2)TPA)Zn(ONHC(O)CH(3))](ClO(4))(2) (11), all of which were characterized by X-ray crystallography. The Mn(II) complex 8.0.75CH(3)()CN.0.75Et(2)()O exhibits a dinuclear structure with bridging hydroxamate ligands, whereas the Co(II), Ni(II), and Zn(II) derivatives all exhibit mononuclear six-coordinate structures with a chelating hydroxamate ligand.     

Syntheses, structures, and reactivities of homometallic rare-earth-metal multimethyl methylidene and oxo complexes

Unsolvated, trinuclear, homometallic, rare-earth-metal multimethyl methylidene complexes [{(NCN)Ln(μ(2)-CH(3))}(3)(μ(3)-CH(3))(μ(3)-CH(2))] (NCN = L = [PhC{NC(6)H(4)(iPr-2,6)(2)}(2)](-); Ln = Sc (2a), Lu (2b)) have been synthesized by treatment of [(L)Ln{CH(2)C(6)H(4)N(CH(3))(2)-o}(2)] (Ln = Sc (1a), Lu (1b)) with two equivalents of AlMe(3) in toluene at ambient temperature in good yields. Treatment of 1 with three equivalents of AlMe(3) gives the heterometallic trinuclear complexes [(L)Ln(AlMe(4))(2)] (Ln = Sc (3a), Lu (3b)) in good yields. Interestingly, 2 can also be generated by recrystallization of 3 in THF/toluene, thereby indicating that the THF molecule can also induce C-H bond activation of 2. Reaction of 2 with one equivalent of ketones affords the trinuclear homometallic oxo-trimethyl complexes [{(L)Ln(μ(2) -CH(3))}(3) (μ(3)-CH(3))(μ(3)-O)] (Ln = Sc(4a), Lu(4b)) in high yields. Complex 4b reacts with one equivalent of cyclohexanone to give the methyl abstraction product [{(L)Lu(μ(2) -CH(3) )}(3) (μ(3) -OC(6)H(9))(μ(3)-O)] (5b), whereas reaction of 4b with acetophenone forms the insertion product [{(L)Lu(μ(2)-CH(3))}(3){μ(3)-OCPh(CH(3))(2)}(μ(3)-O)] (6b). Complex 4a is inert to ketone under the same conditions. All these new complexes have been characterized by elemental analysis, NMR spectroscopy, and confirmed by X-ray diffraction determination.     

2-Aminoisobutyric acid in Co(II) and Co(II)/Ln(III) chemistry: homometallic and heterometallic clusters

The synthesis and magnetic properties of 13 new homo- and heterometallic Co(II) complexes containing the artificial amino acid 2-amino-isobutyric acid, aibH, are reported: [Co(II)(4)(aib)(3)(aibH)(3)(NO(3))](NO(3))(4)·2.8CH(3)OH·0.2H(2)O (1·2.8CH(3)OH·0.2H(2)O), {Na(2)[Co(II)(2)(aib)(2)(N(3))(4)(CH(3)OH)(4)]}(n) (2), [Co(II)(6)La(III)(aib)(6)(OH)(3)(NO(3))(2)(H(2)O)(4)(CH(3)CN)(2)]·0.5[La(NO(3))(6)]·0.75(ClO(4))·1.75(NO(3))·3.2CH(3)CN·5.9H(2)O (3·3.2CH(3)CN·5.9H(2)O), [Co(II)(6)Pr(III)(aib)(6)(OH)(3)(NO(3))(3)(CH(3)CN)(6)]·[Pr(NO(3))(5)]·0.41[Pr(NO(3))(3)(ClO(4))(0.5)(H(2)O)(1.5)]·0.59[Co(NO(3))(3)(H(2)O)]·0.2(ClO(4))·0.25H(2)O (4·0.25H(2)O), [Co(II)(6)Nd(III)(aib)(6)(OH)(3)(NO(3))(2.8)(CH(3)OH)(4.7)(H(2)O)(1.5)]·2.7(ClO(4))·0.5(NO(3))·2.26CH(3)OH·0.24H(2)O (5·2.26CH(3)OH·0.24H(2)O), [Co(II)(6)Sm(III)(aib)(6)(OH)(3)(NO(3))(3)(CH(3)CN)(6)]·[Sm(NO(3))(5)]·0.44[Sm(NO(3))(3)(ClO(4))(0.5)(H(2)O)(1.5)]·0.56[Co(NO(3))(3)(H(2)O)]·0.22(ClO(4))·0.3H(2)O (6·0.3H(2)O), [Co(II)(6)Eu(III)(aib)(6)(OH)(3)(NO(3))(3)(CH(3)OH)(4.87)(H(2)O)(1.13)](ClO(4))(2.5)(NO(3))(0.5)·2.43CH(3)OH·0.92H(2)O (7·2.43CH(3)OH·0.92H(2)O), [Co(II)(6)Gd(III)(aib)(6)(OH)(3)(NO(3))(2.9)(CH(3)OH)(4.9)(H(2)O)(1.2)]·2.6(ClO(4))·0.5(NO(3))·2.58CH(3)OH·0.47H(2)O (8·2.58CH(3)OH·0.47H(2)O), [Co(II)(6)Tb(III)(aib)(6)(OH)(3)(NO(3))(3)(CH(3)CN)(6)]·[Tb(NO(3))(5)]·0.034[Tb(NO(3))(3)(ClO(4))(0.5)(H(2)O)(0.5)]·0.656[Co(NO(3))(3)(H(2)O)]·0.343(ClO(4))·0.3H(2)O (9·0.3H(2)O), [Co(II)(6)Dy(III)(aib)(6)(OH)(3)(NO(3))(2.9)(CH(3)OH)(4.92)(H(2)O)(1.18)](ClO(4))(2.6)(NO(3))(0.5)·2.5CH(3)OH·0.5H(2)O (10·2.5CH(3)OH·0.5H(2)O), [Co(II)(6)Ho(III)(aib)(6)(OH)(3)(NO(3))(3)(CH(3)CN)(6)]·0.27[Ho(NO(3))(3)(ClO(4))(0.35)(H(2)O)(0.15)]·0.656[Co(NO(3))(3)(H(2)O)]·0.171(ClO(4)) (11), [Co(II)(6)Er(III)(aib)(6)(OH)(4)(NO(3))(2)(CH(3)CN)(2.5)(H(2)O)(3.5)](ClO(4))(3)·CH(3)CN·0.75H(2)O (12·CH(3)CN·0.75H(2)O), and [Co(II)(6)Tm(III)(aib)(6)(OH)(3)(NO(3))(3)(H(2)O)(6)]·1.48(ClO(4))·1.52(NO(3))·3H(2)O (13·3H(2)O). Complex 1 describes a distorted tetrahedral metallic cluster, while complex 2 can be considered to be a 2-D coordination polymer. Complexes 3-13 can all be regarded as metallo-cryptand encapsulated lanthanides in which the central lanthanide ion is captivated within a [Co(II)(6)] trigonal prism. dc and ac magnetic susceptibility studies have been carried out in the 2-300 K range for complexes 1, 3, 5, 7, 8, 10, 12, and 13, revealing the possibility of single molecule magnetism behavior for complex 10.     

Towards new organometallic wires: tetraruthenium complexes bridged by phenylenevinylene and vinylpyridine ligands

The tetranuclear complexes [{(PiPr(3))(2)(CO)ClRu(mu-CH=CHpy)Ru Cl(CO)(PPh(3))(2)}(2)(mu-CH=CH-C(6)H(4)- CH=CH-1,4)] (3 a) and [{(PiPr(3))(2)(CO)ClRu(mu-CH=CHpy)RuCl(CO)(PPh(3))(2)}(2)(mu-CH=CH-C(6)H(4)-CH=CH-1,3)] (3b), which contain vinylpyridine ligands that connect peripheral Ru(PiPr(3))(2)(CO)Cl units to a central divinylphenylene-bridged diruthenium core, have been prepared and investigated. These complexes, in various oxidation states up to the tetracation level, have been characterized by standard electrochemical and spectroelectrochemical techniques, including IR, UV/Vis/NIR and ESR spectroscopy. A comparison with the results for the vinylpyridine-bridged dinuclear complex [PiPr(3))(2)(CO)ClRu(mu-CH=CHpy)RuCl(CO)(PPh(3))(2)(CH=CHPh)] (6) and the divinylphenylene-bridged complexes [{(EtOOCpy)(CO)Cl(PPh(3))(2)Ru}(2)(mu-CH=CH-C(6)H(4)-CH=CH-1,4)] (8a) and [{(EtOOCpy)(CO)Cl(PPh(3))(2)Ru}(2)(mu-CH=CH-C(6)H(4)-CH=CH-1,3)] (8b), which represent the outer sections (6) or the inner core (8a,b) of complexes 3a,b, and with the mononuclear complex [(EtOOCpy)(CO)(PPh(3))(2)RuCl(CH=CHPh)] (7) indicate that every accessible oxidation process is primarily centred on one of the vinyl ligands, with smaller contributions from the metal centres. The experimental results and quantum chemical calculations indicate charge- and spin-delocalization across the central divinylphenylenediruthenium part of 3a,b or the styrylruthenium unit of 6, but not beyond. The energy gap between the higher lying styryl- or divinylphenylenediruthenium-based and the lower occupied vinylpyridineruthenium-based orbitals increases in the order 6<3 b<3 a and thus follows the conjugation within the non-heteroatom-substituted aromatic vinyl ligand.     

Thioester hydrolysis reactivity of zinc hydroxide complexes: investigating reactivity relevant to glyoxalase II enzymes

A recently reported binuclear zinc hydroxide complex [(L(1)Zn(2))(mu-OH)](ClO(4))(2) (, L(1) = 2,6-bis[(bis(2-pyridylmethyl)amino)methyl]-4-methylphenolate monoanion) containing a single bridging hydroxide was examined for thioester hydrolysis reactivity. Treatment of it with hydroxyphenylthioacetic acid S-methyl ester in dry CD(3)CN results in no reaction after approximately 65 h at 45(1) degrees C. Binuclear zinc hydroxide complexes of the N-methyl-N-((6-neopentylamino-2-pyridyl)methyl)-N-((2-pyridyl)methyl)amine (L(2)) and N-methyl-N-((6-neopentylamino-2-pyridyl)methyl)-N-((2-pyridyl)ethyl)amine (L(3)) chelate ligands were prepared by treatment of each ligand with molar equivalent amounts of Zn(ClO(4))(2).6H(2)O and KOH in methanol. These complexes, [(L(2)Zn)(2)(mu-OH)(2)](ClO(4))(2) and [(L(3)Zn)(2)(mu-OH)(2)](ClO(4))(2) (), which have been structurally characterized by X-ray crystallography, behave as 1 : 1 electrolytes in acetonitrile, indicating that the binuclear cations dissociate into monomeric zinc hydroxide species in solution. Treatment of them with one equivalent of hydroxyphenylthioacetic acid S-methyl ester per zinc center in acetonitrile results in the formation of a zinc alpha-hydroxycarboxylate complex, [(L(2))Zn(O(2)CCH(OH)Ph)]ClO(4).1.5H(2)O or [(L(3))Zn(O(2)CCH(OH)Ph)]ClO(4).1.5H(2)O, and CH(3)SH. These reactions, to our knowledge, are the first reported examples of thioester hydrolysis mediated by zinc hydroxide complexes. The results of this study suggest that a terminal Zn-OH moiety may be required for hydrolysis reactivity with a thioester substrate.     

Anion binding by metallo-receptors of 5,5'-dicarbamate-2,2'-bipyridine ligands

Three 5,5'-dicarbamate-2,2'-bipyridine ligands (L = L(1)-L(3)) bearing ethyl, isopropyl or tert-butyl terminals, respectively, on the carbamate substituents were synthesized. Reaction of the ligands L with the transition metal ions M = Fe(2+), Cu(2+), Zn(2+) or Ru(2+) gave the complexes ML(n)X(2)·xG (1-12, n = 1-3; X = Cl, NO(3), ClO(4), BF(4), PF(6), ?SO(4); G = Et(2)O, DMSO, CH(3)OH, H(2)O), of which [Fe(L(2))(3)???SO(4)]·8.5H(2)O (2), [Fe(L(1))(3)???(BF(4))(2)]·2CH(3)OH (7), [Fe(L(2))(3)???(Et(2)O)(2)](BF(4))(2)·2CH(3)OH (8), [ZnCl(2)(L(1))][ZnCl(2)(L(1))(DMSO)]·2DMSO (9), [Zn(L(1))(3)???(NO(3))(2)]·2H(2)O (10), [Zn(L(2))(3)???(ClO(4))(Et(2)O)]ClO(4)·Et(2)O·2CH(3)OH·1.5H(2)O (11), and [Cu(L(1))(2)(DMSO)](ClO(4))(2)·2DMSO (12) were elucidated by single-crystal X-ray crystallography. In the complexes ML(n)X(2)·xG the metal ion is coordinated by n = 1, 2 or 3 chelating bipyridine moieties (with other anionic or solvent ligands for n = 1 and 2) depending on the transition metal and reaction conditions. Interestingly, the carbamate functionalities are involved in hydrogen bonding with various guests (anions or solvents), especially in the tris(chelate) complexes which feature the well-organized C(3)-clefts for effective guest inclusion. Moreover, the anion binding behavior of the pre-organized tris(chelate) complexes was investigated in solution by fluorescence titration using the emissive [RuL(3)](2+) moiety as a probe. The results show that fluorescent recognition of anion in solution can be achieved by the Ru(II) complexes which exhibit good selectivities for SO(4)(2-).     

Efficient double-strand cleavage of DNA mediated by Zn(II)-based artificial nucleases

Two water-soluble zinc complexes, [Zn(L)Cl(2)] (1) and [Zn(2)(L)(2)(μ-C(2)O(4))(H(2)O)(2)]·(ClO(4))(2)·CH(3)OH (2) (L = N,N-bis(2-pyridylmethyl)methylamine), were prepared to serve as nuclease mimics. The complexes were characterized by X-ray, IR and UV-vis spectroscopy as well as ESI-MS. The electrospray mass spectrum of 2 in solution indicates that dinuclear ion [Zn(2)(L)(2)(μ-C(2)O(4))(ClO(4))](+) (3) is the active species. UV-Vis absorption and fluorescence spectroscopy studies show that the complexes partially intercalate to CT-DNA. In the absence of reducing agent, supercoiled plasmid DNA cleavage by the complexes 1 and 3 was performed and the hydrolytic mechanism was demonstrated by adding standard radical scavengers.     

Synthesis, structures and photophysical properties of luminescent copper(I) and platinum(II) complexes with a flexible naphthyridine-phosphine ligand

Condensation of Ph(2)PH and paraformaldehyde with 2-amino-7-methyl-1,8-naphthyridine gave the new flexible tridentate ligand 2-[N-(diphenylphosphino)methyl]amino-7-methyl-1,8-naphthyridine (L). Reaction of L with [Cu(CH(3)CN)(4)]BF(4) and/or different ancillary ligands in dichloromethane afforded N,P chelating or bridging luminescent complexes [(L)(2)Cu(2)](BF(4))(2), [(micro-L)(2)Cu(2)(PPh(3))(2)](BF(4))(2) and [(L)Cu(CNN)]BF(4) (CNN = 6-phenyl-2,2'-bipyridine), respectively. Complexes [(L)(2)Pt]Cl(2), [(L)(2)Pt](ClO(4))(2) and [(L)Pt(CNC)]Cl (CNC = 2,6-biphenylpyridine) were obtained from the reactions of Pt(SMe(2))(2)Cl(2) or (CNC)Pt(DMSO)Cl with L. The crystal structures and photophysical properties of the complexes are presented.     

Dinickel(II) complexes: preparation and catalytic activity

Ligands (L(a-c)) based on 2,7-bis(3,5-di-R-pyrazol-1-yl)-1,8-naphthyridine (a, R = H; b, R = CH(3); c, R = Ph) were prepared for the construction of a series of dinickel complexes. Treatment of L(x) with NiCl(2) in an anhydrous methanol/THF solution resulted in the formation of dinuclear complexes [(L(x))(μ-Cl)(2)Ni(2)Cl(2)(CH(3)OH)(2)] (3, x = a; 4, x = b; 5, x = c). These new complexes were characterized by elemental analysis, IR and UV-Vis spectroscopic techniques. The structures of complexes 3 and 4 were further confirmed by X-ray diffraction studies. Interestingly, crystals of 4 were obtained as a co-crystallization of 4 and the methanol substituted species [{(L(b))(μ-Cl)(2)Ni(2)Cl(CH(3)OH)(3)}Cl] (4'). These dinickel complexes have been tested in the catalytic homo-coupling of terminal alkynes with the use O(2) as the oxidant, showing excellent activities. A clear improvement on the catalytic activity of these complexes is observed as compared to the mono-nuclear species.     

Ferromagnetic interaction in mu1,3-cyanamido-derived copper(II) cryptates

The reaction of dinuclear copper(II) cryptates with calcium cyanamide, CaNCN, and sodium dicyanamide, Na[N(CN)(2)] results in dinuclear compounds of formulae [Cu(2)(HNCN)(R3Bm)](ClO(4))(3) (1), [Cu(2)(dca)(R3Bm)](ClO(4))(3)4H(2)O (2), and [Cu(2)(NCNCONH(2))(R3Bm)](CF(3)SO(3))(3) (3), in which R3Bm=N[(CH(2))(2)NHCH(2)(C(6)H(4)-m)CH(2)NH(CH(2))(2)](3)N and dca=dicyanamido ligand (NCNCN(-)). The X-ray diffraction analysis reveals for both 1 and 3 a dinuclear entity in which the copper atoms are bridged by means of the -NCN- unit. The molar magnetic susceptibility measurements of 1-3 in the 2-300 K range indicate ferromagnetic coupling. The calculated J values, by using theoretical methods based on density functional theory (DFT) are in excellent agreement with the experimental data. Catalytic hydration of a nitrile to an amide functional group is assumed responsible for the formation of 3 from a mu(1,3)-dicyanamido ligand.     

Spectroscopic approach in the characterization of the copper(II) complexes of isatin-3,2'-quinolyl-hydrazones and their adducts

Copper(II) complexes of isatin-3,2'-quinolyl-hydrazones of the type [Cu(L)X] (where X=Cl(-), Br(-), NO(3)(-), CH(3)COO(-) and ClO(4)(-)] and their adducts Cu(L)X.2Y [where Y=pyridine or dioxane and X=Cl(-), Br(-), NO(3)(-) and ClO(4)(-)] have been synthesized under controlled experimental conditions and characterized by using the modern spectroscopic and physicochemical techniques viz. IR, electronic, EPR, elemental analysis, magnetic moment susceptibility measurements and molar conductance, etc. On the basis of spectral studies a four coordinated square planer geometry is assigned for Cu(L)X type complexes whereas the adducts (Cu(L)X.2Y were found to have a six coordinated octahedral geometry.     

Entanglement of individual coordination polymers having helicates as building intermediates

A series of Ag(I) coordination compounds, from one-dimensional chains to 3D porous frameworks, were achieved from N,N'-bis[1-(2-pyrazinyl)ethylidene]benzil dihydrazone, L, via self-assembly, using helicates as effective secondary building units. Compound 2 [(Ag(2.75)L)(NO(3))(2.75)] was comprised of two opposite-handed 3D frameworks formed by connecting the 4(1) helical chains into (10(3)-b) nets. The pairs of the racemic 3D frameworks were connected through additional silver(I) centers and entangled each other forming a racemic 3D net. Compound 3 [(Ag(13)L(8))(BF(4))(13)(H(2)O)(12)] was comprised of a 3D framework that was constructed from double-helical building intermediates Ag(2)L(2) with one-dimensional infinite chains being threaded into the large voids of a 3D framework to form a weave structure. The ladder-like chains in compound 4 [(Ag(3)L(2))(ClO(3))(3)(CH(3)OH)(2)(CH(3)CN)] were formed by the addition of excess NaClO(3) into the methanol solution containing AgNO(3) and the ligand L, and the zigzag chains in compound 5 [(Ag(2)L(2))(ClO(4))(2)(CH(3)CN)(2)] were constructed by the addition of excess NaClO(4) into an acetonitrile solution containing AgNO(3) and the ligand L.     

Structural and magnetic studies of Schiff base complexes of nickel(II) nitrite: change in crystalline state, ligand rearrangement and a very rare μ-nitrito-1κO:2κN:3κO' bridging mode

Four new nickel(II) complexes, [Ni(2)L(2)(NO(2))(2)]·CH(2)Cl(2)·C(2)H(5)OH, 2H(2)O (1), [Ni(2)L(2)(DMF)(2)(μ-NO(2))]ClO(4)·DMF (2a), [Ni(2)L(2)(DMF)(2)(μ-NO(2))]ClO(4) (2b) and [Ni(3)L'(2)(μ(3)-NO(2))(2)(CH(2)Cl(2))](n)·1.5H(2)O (3) where HL = 2-[(3-amino-propylimino)-methyl]-phenol, H(2)L(') = 2-({3-[(2-hydroxy-benzylidene)-amino]-propylimino}-methyl)-phenol and DMF = N,N-dimethylformamide, have been synthesized starting with the precursor complex [NiL(2)]·2H(2)O, nickel(ii) perchlorate and sodium nitrite and characterized structurally and magnetically. The structural analyses reveal that in all the complexes, Ni(II) ions possess a distorted octahedral geometry. Complex 1 is a dinuclear di-μ(2)-phenoxo bridged species in which nitrite ion acts as chelating co-ligand. Complexes 2a and 2b also consist of dinuclear entities, but in these two compounds a cis-(μ-nitrito-1κO:2κN) bridge is present in addition to the di-μ(2)-phenoxo bridge. The molecular structures of 2a and 2b are equivalent; they differ only in that 2a contains an additional solvated DMF molecule. Complex 3 is formed by ligand rearrangement and is a one-dimensional polymer in which double phenoxo as well as μ-nitrito-1κO:2κN bridged trinuclear units are linked through a very rare μ(3)-nitrito-1κO:2κN:3κO' bridge. Analysis of variable-temperature magnetic susceptibility data indicates that there is a global weak antiferromagnetic interaction between the nickel(ii) ions in four complexes, with exchange parameters J of -5.26, -11.45, -10.66 and -5.99 cm(-1) for 1, 2a, 2b and 3, respectively.     

Syntheses, structures and properties of a series of non-heme alkoxide-Fe(III) complexes of a benzimidazolyl-rich ligand as models for lipoxygenase

The treatment of Fe(ClO(4))(2)·6H(2)O or Fe(ClO(4))(3)·9H(2)O with a benzimidazolyl-rich ligand, N,N,N',N'-tetrakis[(1-methyl-2-benzimidazolyl)methyl]-1,2-ethanediamine (medtb) in alcohol/MeCN gives a mononuclear ferrous complex, [Fe(II)(medtb)](ClO(4))(2)·?CH(3)CN·?CH(3)OH (1), and four non-heme alkoxide-iron(III) complexes, [Fe(III)(OMe)(medtb)](ClO(4))(2)·H(2)O (2, alcohol = MeOH), [Fe(III)(OEt)(Hmedtb)](ClO(4))(3)·CH(3)CN (3, alcohol = EtOH), [Fe(III)(O(n)Pr)(Hmedtb)](ClO(4))(3)·(n)PrOH·2CH(3)CN (4, alcohol = n-PrOH), and [Fe(III)(O(n)Bu)(Hmedtb)](ClO(4))(3)·3CH(3)CN·H(2)O (5, alcohol = n-BuOH), respectively. The alkoxide-iron(III) complexes all show 1) a Fe(III)-OR center (R = Me, 2; Et, 3; (n)Pr, 4; (n)Bu, 5) with the Fe-O bond distances in the range of 1.781-1.816 ?, and 2) a yellow color and an intense electronic transition around 370 nm. The alkoxide-iron(III) complexes can be reduced by organic compounds with a cis,cis-1,4-diene moiety via the hydrogen atom abstraction reaction.     

Self-assembled hetero-bimetallic coordination cage and cation-clusters with micro(2)-Cl bridging using a flexible two-arm ferrocene amide linker

One flexible, discrete coordination cage [Cu(2)(3-BPFA)(4)(H(2)O)(2)](ClO(4))(4).4CH(3)OH (), and two cation-clusters with micro(2)-Cl bridging [Ni(2)(micro-Cl)(3-BPFA)(4)(H(2)O)(2)](ClO(4))(3) () and [Co(2)(micro-Cl)(3-BPFA)(4)(H(2)O)(2)](ClO(4))(4).4CH(3)OH (), containing the ferrocenyl functionality were prepared via coordination-driven self-assembly and Cl-anion template from Cu(II), Ni(II) and Co(II) salts and a flexible two-arm molecule 1,1-bis[(3-pyridylamino)carbonyl]ferrocene (3-BPFA).     

Platinum and palladium imido and oxo complexes with small natural bite angle diphosphine ligands

Treatment of L(2)MCl(2) (M = Pt, Pd; L(2) = Ph(2)PCMe(2)PPh(2) (dppip), Ph(2)PNMePPh(2) (dppma)) with AgX (X = OTf, BF(4), NO(3)) in wet CH(2)Cl(2) yields the dinuclear dihydroxo complexes [L(2)M(mu-OH)](2)(X)(2), the mononuclear aqua complexes [L(2)M(OH(2))(2)](X)(2), the mononuclear anion complexes L(2)MX(2), or mixtures of complexes. Addition of aromatic amines to these complexes or mixtures gives the dinuclear diamido complexes [L(2)Pt(mu-NHAr)](2)(BF(4))(2), the mononuclear amine complexes [L(2)M(NH(2)Ar)(2)](X)(2), or the dinuclear amido-hydroxo complex [Pt(2)(mu-OH)(mu-NHAr)(dppip)(2)](BF(4))(2). Deprotonation of the Pd and Pt amine or diamido complexes with M'N(SiMe(3))(2) (M' = Li, Na, K) gives the diimido complexes [L(2)M(mu-NAr)](2) associated with M' salts. Structural studies of the Li derivatives indicate association through coordination of the imido nitrogen atoms to Li(+). Deprotonation of the amido-hydroxo complex gives the imido-oxo complex [Pt(2)(mu-O)(mu-NAr)(dppip)(2)].LiBF(4).LiN(SiMe(3))(2), and deprotonation of the dppip Pt hydroxo complex gives the dioxo complex [Pt(mu-O)(dppip)](2).LiN(SiMe(3))(2).2LiBF(4).     

Monomeric oxovanadium(IV) compounds of the general formula cis-[V(IV)(=O)(X)(L(NN))(2)](+/0) [X = OH(-), Cl(-), SO(4)(2)(-) and L(NN) = 2,2'-bipyridine (bipy) or 4,4'-disubstituted bipy

Reaction of [V(IV)OCl(2)(THF)(2)] in aqueous solution with 2 equiv of AgBF(4) or AgSbF(6) and then with 2 equiv of 2,2'-bipyridine (bipy), 4,4'-di-tert-butyl-2,2'-bipyridine (4,4'-dtbipy), or 4,4'-di-methyl-2,2'-bipyridine (4,4'-dmbipy) affords compounds of the general formula cis-[V(IV)O(OH)(L(NN))(2)]Y [where L(NN) = bipy, Y = BF(4)(-) (1), L(NN) = 4,4'-dtbipy, Y = BF(4)(-) (2.1.2H(2)O), L(NN) = 4,4'-dmbipy, Y = BF(4)(-) (3.2H(2)O), and L(NN) = 4,4'-dtbipy, Y = SbF(6)(-) (4)]. Sequential addition of 1 equiv of Ba(ClO(4))(2) and then of 2 equiv of bipy to an aqueous solution containing 1 equiv of V(IV)OSO(4).5H(2)O yields cis-[V(IV)O(OH)(bipy)(2)]ClO(4) (5). The monomeric compounds 1-5 contain the cis-[V(IV)O(OH)](+) structural unit. Reaction of 1 equiv of V(IV)OSO(4).5H(2)O in water and of 1 equiv of [V(IV)OCl(2)(THF)(2)] in ethanol with 2 equiv of bipy gives the compounds cis-[V(IV)O(OSO(3))(bipy)(2)].CH(3)OH.1.5H(2)O (6.CH(3)OH.1.5H(2)O) and cis-[V(IV)OCl(bipy)(2)]Cl (7), respectively, while reaction of 1 equiv of [V(IV)OCl(2)(THF)(2)] in CH(2)Cl(2) with 2 equiv of 4,4'-dtbipy gives the compound cis-[V(IV)OCl(4,4'-dtbipy)(2)]Cl.0.5CH(2)Cl(2) (8.0.5CH(2)Cl(2)). Compounds cis-[V(IV)O(BF(4))(4,4'-dtbipy)(2)]BF(4) (9), cis-[V(IV)O(BF(4))(4,4'-dmbipy)(2)]BF(4) (10), and cis-[V(IV)O(SbF(6))(4,4'-dtbipy)(2)]SbF(6) (11) were synthesized by sequential addition of 2 equiv of 4,4'-dtbipy or 4,4'-dmbipy and 2 equiv of AgBF(4) or AgSbF(6) to a dichloromethane solution containing 1 equiv of [V(IV)OCl(2)(THF)(2)]. The crystal structures of 2.1.2H(2)O, 6.CH(3)OH.1.5H(2)O, and 8.0.5CH(2)Cl(2) were demonstrated by X-ray diffraction analysis. Crystal data are as follows: Compound 2.1.2H(2)O crystallizes in the orthorhombic space group Pbca with (at 298 K) a = 21.62(1) A, b = 13.33(1) A, c = 27.25(2) A, V = 7851(2) A(3), Z = 8. Compound 6.CH(3)OH.1.5H(2)O crystallizes in the monoclinic space group P2(1)/a with (at 298 K) a = 12.581(4) A, b = 14.204(5) A, c = 14.613(6) A, beta = 114.88(1) degrees, V = 2369(1), Z = 4. Compound 8.0.5CH(2)Cl(2) crystallizes in the orthorhombic space group Pca2(1) with (at 298 K) a = 23.072(2) A, b = 24.176(2) A, c = 13.676(1) A, V = 7628(2) A(3), Z = 8 with two crystallographically independent molecules per asymmetric unit. In addition to the synthesis and crystallographic studies, we report the optical, infrared, magnetic, conductivity, and CW EPR properties of these oxovanadium(IV) compounds as well as theoretical studies on [V(IV)O(bipy)(2)](2+) and [V(IV)OX(bipy)(2)](+/0) species (X = OH(-), SO(4)(2)(-), Cl(-)).     

Mononuclear and dinuclear palladium and nickel complexes of phosphinimine-based tridentate ligands

The tridentate bis-phosphinimine ligands O(1,2-C(6)H(4)N=PPh(3))(2)1, HN(1,2-C(2)H(4)N=PR(3))(2) (R = Ph 2, iPr 3), MeN(1,2-C(2)H(4)N=PPh(3))(2)4 and HN(1,2-C(6)H(4)N=PPh(3))(2)5 were prepared. Employing these ligands, monometallic Pd and Ni complexes O(1,2-C(6)H(4)N=PPh(3))(2)PdCl(2)6, RN(1,2-CH(2)CH(2)N=PPh(3))(2)PdCl][Cl] (R = H 7, Me 8), [HN(1,2-CH(2)CH(2)N=PiPr(3))(2)PdCl][Cl] 9, [MeN(1,2-CH(2)CH(2)N=PPh(3))(2)PdCl][PF(6)] 10, [HN(1,2-CH(2)CH(2)N=PPh(3))(2)NiCl(2)] 11, [HN(1,2-CH(2)CH(2)N=PR(3))(2)NiCl][X] (X = Cl, R = iPr 12, X = PF(6), R = Ph 13, iPr 14), and [HN(1,2-C(6)H(4)N=PPh(3))(2)Ni(MeCN)(2)][BF(4)]Cl 15 were prepared and characterized. While the ether-bis-phosphinimine ligand 1 acts in a bidentate fashion to Pd, the amine-bis-phosphinimine ligands 2-5 act in a tridentate fashion, yielding monometallic complexes of varying geometries. In contrast, initial reaction of the amine-bis-phosphinimine ligands with base followed by treatment with NiCl(2)(DME), afforded the amide-bridged bimetallic complexes N(1,2-CH(2)CH(2)N=PR(3))(2)Ni(2)Cl(3) (R = Ph 16, iPr 17) and N(1,2-C(6)H(4)N=PPh(3))(2)Ni(2)Cl(3)18. The precise nature of a number of these complexes were crystallographically characterized.