Facile synthesis of Cu(II) complexes of monocondensed N,N,N donor Schiff base ligands: crystal structure, spectroscopic and magnetic properties

Four new copper(II) complexes, [((CuLN3)-N-1)(2)](ClO4)(2) (1), [(CuL2 N-3)(2)](ClO4)(2) (2), [CuL3(N-3)ClO4)](n) (3) and [CuL4(mu-1,1-N-3)(mu-1,3-N-3)(ClO4)](n) (4) where L-1 = N-1-pyridin-2-yl-methylene-propane-1,3-diamine, L-2 = N-1-(1-pyridin-2-yl-ethylidene)propane-1,3-diamine, L-3 =N-1-(1-pyridin-2-yl-ethylidene)ethane-1,2-diamine and L-4=N-1-(1-pyridin-2-yl-ethylidene)propane-1,2-diamine are four tridentate N,N,N donor Schiff base ligands, have been derived and structurally characterized by X-ray crystallography. Compounds 1 and 2 consist of double basal-apical end-on (EO) azide bridged dinuclear Cu-II complexes with square-pyramidal geometry. In complex 3 the square planar mononuclear [CuL3 (N-3)] units are linked by weakly coordinated perchlorate ions in the axial positions of Cu-II to form a one-dimensional chain. Two such chains are connected by hydrogen bonds involving perchlorate ions and azide groups. Compound 4 consists of 1-D chains in which the Cu-II ions with a square-pyramidal geometry are alternately bridged by single EO and end-to-end (EE) azido ligands, both adopting a basal-apical disposition. Variable temperature (300-2 K) magnetic susceptibility measurements and magnetization measurements at 2 K have been performed. The results reveal that complexes 1 and 2 are antiferromagnetically coupled through azido bridges (J= -12.18 +/- 0.09 and -4.43 +/- 0.1 cm(-1) for 1 and 2, respectively). Complex 3 shows two different magnetic interactions through the two kinds of hydrogen bonds; one is antiferromagnetic (J(1) = - 9.69 +/- 0.03 cm(-1)) and the other is ferromagnetic (J(2) = 1.00 +/- 0.01 cm(-1)). From a magnetic point of view complex 4 is a ferromagnetic dinuclear complex (J= 1.91 +/- 0.01 cm(-1)) coupled through the EO bridge only. The coupling through the EE bridge is practically nil as the N(azido)-Cu-II (axial) distance (2.643 angstrom) is too long. (C) 2006 Elsevier Ltd. All rights reserved.

Nickel(II) complexes of tetradentate NSNO pyridylthioazophenol ligands: synthesis, characterization and crystal structure

Two sets of nickel(11) complexes of a series of tetradentate NSNO ligands were synthesized and isolated in their pure form. All these complexes, formulated as [Ni(L)Cl](2) and [Ni(L)(N-3)](2) [HL = pyridylthioazophenols], were characterized using physicochemical and spectroscopic tools. The solid-state structures of two complexes (1a and 2a) were established by X-ray crystallography. The geometry about the nickel ion of the complexes is octahedral and the complexes are dimeric in nature. In 1, two Ni(II) ions are bridged by two Cl- anions while in 2 they are bridged by two azide ions in a mu-1,1-bridging fashion. (C) 2008 Elsevier Ltd. All rights reserved.

Stereochemically non-rigid helical mercury(II) complexes

Reactions of the 1: 2 condensate (L) of benzil dihydrazone and 2-acetylpyridine with Hg(ClO4)(2) center dot xH(2)O and HgI2 yield yellow [HgL2](ClO4)(2) (1) and HgLI2 (2), respectively. Homoleptic 1 is a 8-coordinate double helical complex with a Hg(II)N-8 core crystallising in the space group Pbca with cell dimensions: a = 16.2250(3), b = 20.9563(7), c = 31.9886(11) angstrom. Complex 2 is a 4-coordinate single helical complex having a Hg(II)N2I2 core crystallising in the space group P2(1)/n with cell dimensions a = 9.8011(3), b = 17.6736(6), c = 16.7123(6) angstrom and b = 95.760(3). In complex 1, the N-donor ligand L uses all of its binding sites to act as tetradentate. On the other hand, it acts as a bidentate N-donor ligand in 2 giving rise to a dangling part. From variable temperature H-1 NMR studies both the complexes are found to be stereochemically non-rigid in solution. In the case of 2, the solution process involves wrapping up of the dangling part of L around the metal. (C) 2008 Elsevier B.V. All rights reserved.

Square planar mononuclear Pd(II) complexes of substituted 2-(pyrazole-1-yl)phenylamines with a helical twist

X-ray crystal structure shows that 3,5-dimethyl-1-(2-nitrophenyl)-1H-pyrazole (DNP) belongs to the rare class of helically twisted synthetic organic molecules. Hydrogenation of DNP gives 2-(3,5-dimethylpyrazole-1-yl)phenylamine (L) which on methylation yields [2-(3,5-dimethylpyrazole-1-yl)phenyl]dimethylamine (L'). Two Pd(II) complexes, PdLCl2 (1) and PdL'Cl-2 (2), are synthesized and characterized by NMR. X-ray crystallography reveals that 1 and 2 are unprecedented square planar complexes which possess well discernible helical twists. (C) 2007 Elsevier B.V. All rights reserved.

Two pentacoordinate copper(II) complexes that display accessible Cu(III/II) couples

Two copper(II) complexes of the type CuL2.imidazole (1) and Cu2L4(4.4'-bpy).2H(2)O.C6H14 (2), where LH = 1-nitroso-2-naphthol and 4.4'-bpy = 4,4'-bipyridine, are characterised by X-ray crystallography. In 2, the two copper atoms are linked by 4,4'-bpy. In both the complexes, copper is found to have a distorted square pyramidal N3O2 coordination sphere. The axial position in I is occupied by an oxygen atom while those in 2 by the nitrogen atoms of 4.4'-bpy. The two complexes display quasireversible Cu(III/II) couples around 0.68 V vs. saturated calomel electrode in cyclic voltammetry in dichloromethane.

Zinc(II) mediated synthesis of an N-substituted 2-(2-pyridyl)imidazole from a 1,2-diketone and 2-(aminomethyl)pyridine and its ligational behaviour

Reaction of anhydrous ZnCl2 with the 1:2 condensate (L) of benzil and 2-(aminomethyl)pyridine in methanol gives monomeric ZnL'Cl-2 (1) where L' is 2-[(4,5-diphenyl-2-pyridin-2-yl-1H-imidazol-1-yl)-methyl]pyridine. In the X-ray crystal structure, 1 is found to contain tetrahedral zinc with an N2Cl2 coordination sphere and the N-substituent methylpyridine fragment hanging as a free arm. A tentative mechanism is proposed for the zinc mediated conversion of L-->L'. Demetallation of 1 by the action of aqueous NaOH yields L' in the free state. When L' is reacted with Zn(ClO4)(2).6H(2)O in a 1:2 molar proportion, [Zn(L')(2)](n)(ClO4)(2n).(H2O)(n/2).(CH2Cl2)(n/2) (2) is obtained. The zinc atom in 2, as revealed by X-ray crystallography, has a trigonal bipyramidal N-5 coordination sphere. There are two independent ligands in the asymmetric unit of 2. One of them bonds only to one zinc atom in a bidentate mode with the N-substituent methylpyridine hanging free while the other ligand binds to two different zinc atoms in a tridentate fashion, employing the N-substituent methylpyridine nitrogen atom to form the polymeric one-dimensional chain cation.

Two new Ni-II complexes with mu(1.5)-dicyanamide as bridging ligand

One 3D and one 2D mu(1,5)-dicyanamide bridged Ni-II complexes having molecular formula [Ni(L1)(dca)(2)] (1) and [Ni-2(L-2)(2)(dca)(4)] (.) 0.5H(2)O (2) (L1 = 4-(2-aminoethyl)-morpholine, L2 = 1-(2-aminoethyl)-piperidine and dca = dicyanamide dianion) have been synthesized. X-ray single crystal analyses and low temperature magnetic measurements were used to characterize the complexes. Complex 1 represents a 3D structure where each metal ion is chelated by morpholine ligand (L1) and connected by four mu(1,5)-dca. Whereas complex 2 shows an undulated 2D structure with grid of (4,4) topology having two crystallographically independent Ni-II centers in similar octahedral environment where each metal center is chelated by one piperidine ligand (L2) and coordinated by four mu(1,5)-dca. Magnetic measurements of both the complexes indicate weak antiferromagnetic interactions through the mu-(1,5)-dca bridging ligands. (c) 2004 Elsevier B.V. All rights reserved.

Syntheses, structural analyses, and magneto-structural correlations of three polymeric Fe(II) complexes with azide ligand

Three new metal-organic polymeric complexes, [Fe(N-3)(2)(bPP)(2)] (1), [Fe(N-3)(2)(bpe)] (2), and [Fe(N-3)(2)(phen)] (3) [bpp = (1,3-bis(4-pyridyl)-propane), bpe = (1,2-bis(4-pyridyl)-ethane), phen = 1,10-phenanthroline], have been synthesized and characterized by single-crystal X-ray diffraction studies and low-temperature magnetic measurements in the range 300-2 K. Complexes 1 and 2 crystallize in the monoclinic system, space group C2/c, with the following cell parameters: a = 19.355(4) Angstrom, b = 7.076(2) Angstrom, c = 22.549(4) Angstrom, beta = 119.50(3)degrees, Z = 4, and a = 10.007(14) Angstrom, b = 13.789(18) Angstrom, c = 10.377(14) Angstrom, beta = 103.50(1)degrees, Z = 4, respectively. Complex 3 crystallizes in the triclinic system, space group P (1) over bar, with a = 7.155(12) Angstrom, b = 10.066(14) Angstrom, c = 10.508(14) Angstrom, alpha = 109.57(1)degrees, beta = 104.57(1)degrees, gamma = 105.10(1)degrees, and Z = 2. All coordination polymers exhibit octahedral Fe(II) nodes. The structural determination of 1 reveals a parallel interpenetrated structure of 2D layers of (4,4) topology, formed by Fe(II) nodes linked through bpp ligands, while mono-coordinated azide anions are pendant from the corrugated sheet. Complex 2 has a 2D arrangement constructed through 1D double end-to-end azide bridged iron(11) chains interconnected through bpe ligands. Complex 3 shows a polymeric arrangement where the metal ions are interlinked through pairs of end-on and end-to-end azide ligands exhibiting a zigzag arrangement of metals (Fe-Fe-Fe angle of 111.18degrees) and an intermetallic separation of 3.347 Angstrom (through the EO azide) and of 5.229 Angstrom (EE azide). Variable-temperature magnetic susceptibility data suggest that there is no magnetic interaction between the metal centers in 1, whereas in 2 there is an antiferromagnetic interaction through the end-to-end azide bridge. Complex 3 shows ferro- as well as anti-ferromagnetic interactions between the metal centers generated through the alternating end-on and end-to-end azide bridges. Complex I has been modeled using the D parameter (considering distorted octahedral Fe(II) geometry and with any possible J value equal to zero) and complex 2 has been modeled as a one-dimensional system with classical and/or quantum spin where we have used two possible full diagonalization processes: without and with the D parameter, considering the important distortions of the Fe(II) ions. For complex 3, the alternating coupling model impedes a mathematical solution for the modeling as classical spins. With quantum spin, the modeling has been made as in 2.

Intermediate ion stability and regio selectivity polymerization using neutral salicyladiminato in propene nickel(II) and palladium(II) complexes as catalysts

The mechanism of the Heck reaction has been studied with regard to transition metal catalysis of the addition of propene and the formation of unsaturated polymers. The reactivity of nickel and palladium complexes with five different bidentate ligands with O,N donor atoms has been investigated by computational methods involving density functional theory. Hence, it is possible to understand the electronic and steric factors affecting the reaction and their relative importance in determining the products formed in regard of their control of the regiochemistry of the products. Our results show that whether the initial addition of propene is trans to O or to N of the bidentate ligand is of crucial importance to the subsequent reactions. Thus when the propene is trans to 0, 1,2-insertion is favoured, but when the propene is trans to N, then 2,1-insertion is favoured. This difference in the preferred insertion pathway can be related to the charge distribution engendered in the propene moiety when the complex is formed. Indeed charge effects are important for catalytic activity but also for regioselectivity. Steric effects are shown to be of lesser importance even when t-butyl is introduced into the bidentate ligand as a substituent. (C) 2007 Elsevier B.V. All rights reserved.

Syntheses, characterization and X-ray crystal structures of Ni(II) complexes of tridentate monocondensed and tetradentate dicondensed Schiff bases

Two octahedral complexes [Ni(HL1)(2)](ClO4)(2) (1) and [Ni(HL2)(2)](ClO4)(2) (2) and a square planar complex [Ni(HL3)]ClO4 (3) have been prepared, where [HL1 = 3-(2-amino-ethylimino)-butan-2-one oxime, HL2 = 3-(2-amino-propylimino)butan-2-one oxime] and H2L3 = 3-[2-(3-hydroxy-1-methyl-but-2-enylideneamino)-1-methyl-ethylimino]-buta n-2-one oxime. All the complexes have been characterized by elemental analyses, spectral studies and room temperature magnetic moment measurements. The molecular structures of all three compounds were elucidated on the basis of X-ray crystallography: complexes 1 and 2 are seen to be the met isomers. (C) 2008 Elsevier Ltd. All rights reserved.

Tuning of redox potential and visible absorption band of ruthenium(II) complexes of (benzimidazolyl) derivatives: synthesis, characterization, spectroscopic and redox properties, X-ray structures and DFT calculations

Six ruthenium(II) complexes have been prepared using the tridentate ligands 2,6-bis(benzimidazolyl) pyridine and bis(2-benzimidazolyl methyl) amine and having 2,2'-bipyridine, 2,2':6',2 ''-terpyridine, PPh3, MeCN and chloride as coligands. The crystal structures of three of the complexes trans-[Ru(bbpH(2))(PPh3)(2)(CH3CN)I(ClO4)(2) center dot 2H(2)O (2), [Ru(bbpH(2))(bpy)Cl]ClO4 (3) and [Ru(bbpH(2))(terpy)](ClO4)(2) (4) are also reported. The complexes show visible region absorption at 402-517 nm, indicating that it is possible to tune the visible region absorption by varying the ancillary ligand. Luminescence behavior of the complexes has been studied both at RT and at liquid nitrogen temperature (LNT). Luminescence of the complexes is found to be insensitive to the presence of dioxygen. Two of the complexes [Ru(bbpH(2))(bpy)Cl]ClO4 (3) and [Ru(bbpH(2))(terpy]ClO4)(2) (4) show RT emission in the NIR region, having lifetime, quantum yield and radiative constant values suitable for their application as NIR emitter in the solid state devices. The DFT calculations on these two complexes indicate that the metal t(2g) electrons are appreciably delocalized over the ligand backbone. (C) 2006 Elsevier B.V. All rights reserved.

Mononuclear and binuclear ruthenium(II) complexes with 4-(phenyl) thiosemicarbazone of benzaldehyde: a discussion on the relative stabilities of the four-membered and five-membered chelate rings formed by the ligand

Three new ruthenium complexes of the formulae cis-[Ru(PPh3)(2)(BzTscbz)(2)] (1a), [Ru-2(PPh3)(2)(BzTscbz)(4)] (1b) and [Ru(PPh3)(2)(BzTscHbz)(2)](ClO4)(2) (2) [BzTscHbz = 4-(phenyl) thiosemicarbazone of benzaldehyde] have been synthesized and characterized by various physicochemical methods including X-ray structure determinations for 1a and 1b. The relative stabilities of the four-membered versus five-membered chelate rings formed by the deprotonated ligand BzTscbz are discussed on the basis of the experimental results and some semi-empirical as well as DFT calculations. (c) 2005 Elsevier Ltd. All rights reserved.

Structural variations in Ni(II) complexes of salen type di-Schiff base ligands

Three di-Schiff-base ligands, N,N'-bis(salicylidene)-1,3-propanediamine (H(2)Salpn), N,N'-bis(salicylidene)-1,3-pentanedianiine (H(2)Salpen) and N,N'-bis(salicylidine)-ethylenediamine (H(2)Salen) react with Ni(SCN)(2). 4H(2)O in 2:3 molar ratios to form the complexes; mononuclear [Ni(HSalpn)(NCS)(H2O)]center dot H2O (1a), trinuclear [{Ni(Salpen)}(2)Ni(NCS)(2)] (2b) and trinuclear [{Ni(Salen)}(2)Ni(NCS)(2)] (3) respectively. All the complexes have been characterized by elemental analyses, IR and UV-VIS spectra, and room temperature magnetic susceptibility measurements. The structures of la and 2b have been confirmed by X-ray single crystal analysis. In complex la, the Ni(II) atom is coordinated equatorially by the tetradentate, mononegative Schiff-base, HSalpn. Axial coordination of isothiocyanate group and a water molecule completes its octahedral geometry. The hydrogen atom attached to one of the oxygen atoms of the Schiff base is involved in a very strong hydrogen bond with a neighboring unit to form a centrosymmetric dimer. In 2b, two square planar [Ni(Salpen)] units act as bide mate oxygen donor ligands to a central Ni(II) which is also coordinated by two mutually cis N-bonded thiocyanate ligands to complete its distorted octahedral geometry. Complex 3 possesses a similar structure to that of 2b. A dehydrated form of la and a hydrated form of 2b have been obtained and characterized. The importance of electronic and steric factors in the variation of the structures is discussed. (c) 2007 Elsevier Ltd. All rights reserved.

Influence of counter anions on the structures and magnetic properties of trinuclear Cu(II) complexes containing a mu(3)-OH core and Schiff base ligands

Four trinuclear Cu(II) complexes, [(CuL1)(3)(mu(3)-OH)](NO3)(2) (1), [(CuL2)(3)(mu(3)-OH)](I)(2)center dot H2O (2), [(CuL3)(3)(mu(3)-OH)](I)(2) (3) and [(CuL1)(3)(mu(3)-OH)][(CuI3)-I-1] (4), where HL1 (8-amino-4-methyl-5-azaoct-3-en-2-one), HL2 [7-amino-4-methyl-5-azaoct-3-en-2-one] and HL3 [7-amino-4-methyl-5-azahept-3-en-2- one] are the three tridentate Schiff bases, have been synthesized and structurally characterized by X-ray crystallography. All four complexes contain a partial cubane core, [(CuL)(3)(mu(3)-OH)](2+) in which the three [CuL] subunits are interconnected through two types of oxygen bridges afforded by the oxygen atoms of the ligands and the central OH- group. The copper(II) ions are in a distorted square-pyramidal environment. The equatorial plane consists of the bridging oxygen of the central OH- group together with three atoms (N, N, O) from the Schiff base. The oxygen atom of the Schiff base also coordinates to the axial position of Cu(II) of another subunit to form the cyclic trimer. Magnetic susceptibilities have been determined for these complexes over the temperature range of 2-300 K. The isotropic Hamiltonian, H = -J(12)S(1)S(2) - J(13)S(1)S(3) - J(23)S(2)S(3) has been used to interpret the magnetic data. The best fit parameters obtained are: J = - 54.98 cm(-1) g = 2.24 for 1; J = - 56.66 cm(-1), g = 2.19 for 2; J = -44.39 cm(-1), g = 2.16 for 3; J = - 89.92 cm(-1), g = 2.25 for 4. The EPR data at low temperature indicate that the phenomenon of spin frustration occurs for complexes 1-3. (c) 2007 Elsevier B.V. All rights reserved.

Anion-directed template synthesis and hydrolysis of mono-condensed Schiff base of 1,3-pentanediamine and o-hydroxyacetophenone in Ni-II and Cu-II complexes

Bis(o-hydroxyacetophenone)nickel(II) dihydrate, on reaction with 1,3-pentanediamine, yields a bis-chelate complex [NiL2]center dot 2H(2)O (1) of mono-condensed tridentate Schiff base ligand HL {2-[1-(3-aminopentylimino)ethyl]phenol}. The Schiff base has been freed from the complex by precipitating the Nil, as a dimethylglyoximato complex. HL reacts smoothly with Ni(SCN)(2)center dot 4H(2)O furnishing the complex [NiL(NCS)] (2) and with CuCl2 center dot 2H(2)O in the presence of NaN3 or NH4SCN producing [CuL(N-3)](2) (3) or [CuL(NCS)] (4). On the other hand, upon reaction with Cu(ClO4)(2)center dot 6H(2)O and Cu(NO3)(2)center dot 3H(2)O, the Schiff base undergoes hydrolysis to yield ternary complexes [Cu(hap)(pn)(H2O)]ClO4 (5) and [Cu(hap)(pn)(H2O)]NO3 (6), respectively (Hhap = o-hydroxyacetophenone and pn = 1,3-pentanediamine). The ligand HL undergoes hydrolysis also on reaction with Ni(ClO4)(2)center dot 6H(2)O or Ni(NO3)(2)center dot 6H(2)O to yield [Ni(hap)(2)] (7). The structures of the complexes 2, 3, 5, 6, and 7 have been confirmed by single-crystal X-ray analysis. In complex 2, Ni-II possesses square-planar geometry, being coordinated by the tridentate mono-negative Schiff base, L and the isothiocyanate group. The coordination environment around Cu-II in complex 3 is very similar to that in complex 2 but here two units are joined together by end-on, axial-equatorial azide bridges to result in a dimer in which the geometry around Cu-II is square pyramidal. In both 5 and 6, the Cu-II atoms display the square-pyramidal environment; the equatorial sites being coordinated by the two amine groups of 1,3-pentanediamine and two oxygen atoms of o-hydroxyacetophenone. The axial site is coordinated by a water molecule. Complex 7 is a square-planar complex with the Ni atom bonded to four oxygen atoms from two hap moieties. The mononuclear units of 2 and dinuclear units of 3 are linked by strong hydrogen bonds to form a one-dimensional network. The mononuclear units of 5 and 6 are joined together to form a dimer by very strong hydrogen bonds through the coordinated water molecule. These dimers are further involved in hydrogen bonding with the respective counteranions to form 2-D net-like open frameworks. ((C) Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2008).