CuII2, CuII4 and CuII6 complexes with 3-(2-pyridyl)pyrazolate. Structure, magnetism and core interconversion

Abstract Reactions of stoichiometric amounts of L1(−) (HL1 = 3-(2-pyridyl)pyrazole) with [Cu(H2O)6](ClO4)2, with or without PhCO2−, in MeOH or N,N′-dimethylformamide (dmf), led to the isolation of three copper(II) complexes of varying nuclearity, [CuII2(L1)2(ClO4)2(MeOH)2] (1), [CuII4(L1)4(O2CPh)2(MeOH)4](ClO4)2·2H2O (2) and [CuII6(L1)6(O2CPh)2(ClO4)2(dmf)4](ClO4)2·2dmf·2H2O (3). Structural analysis reveals two centrosymmetric four-coordinate {CuII(L1)(ClO4)(MeOH)} units are dipyrazolate-bridged in 1, giving rise to a square-pyramidal (SP; τ = 0.13) coordination to the CuII ion. In 2, two centrosymmetric four-coordinate dipyrazolate-bridged {CuII2(μ-L1)2(MeOH)2}2+ units in two layers are he…

Discrete and 1D coordination polymeric chloro-bridged copper(II) dimers exhibiting ferro- and antiferromagnetic exchange coupling: Magneto-structural correlations and non-covalent interactions

The synthesis and characterization of two 1D coordination polymers [Cu 2 (MHL)Cl 2 ][ClO 4 ] 2  · CH 3 CN · THF ( 2  · CH 3 CN · THF) and [Cu 2 (MPyPz)Cl 2 ][ClO 4 ] 2  · CH 3 CN ( 3  · CH 3 CN), having repetitive { Cu 2 II ( μ -Cl ) 2 } units, of m -xylyl-based ligands with terminal tridentate (2-pyridyl)alkylamine (MHL = α,α′-bis[ N -(2-pyridylethyl)- N -(2-pyridylmethyl)amino]- m -xylene) and (2-pyridyl)alkylamine/pyrazole (MPyPz = α,α′-bis[ N -(2-pyridylethyl)- N -(pyrazol-1-ylmethyl)amino]- m -xylene) coordination have been accomplished. X-ray crystallographic studies reveal that the copper(II) centers in the recently reported dichloro-bridged discrete { Cu 2 II ( μ -Cl ) 2 } complex […

[CuII{(LISQ)˙−}2] (H2L: thioether-appended o-aminophenol ligand) monocation triggers change in donor site from N2O2 to N2O(2)S and valence-tautomerism

Using a potentially tridentate o-aminophenol-based redox-active ligand H2L1 (2-[2-(benzylthio)phenylamino]-4,6-di-tert-butylphenol) in its deprotonated form, [Cu(L1)2] has been synthesized and crystallized as [CuII(L1)2]·CH2Cl2 (1·CH2Cl2). A cyclic voltammetry experiment (in CH2Cl2; V vs. SCE (saturated calomel electrode)) on 1·CH2Cl2 exhibits two oxidative (E = 0.20 V (peak-to-peak separation, ΔEp = 100 mV) and E = 0.90 V (ΔEp = 140 mV)) and two reductive (E = -0.52 V (ΔEp = 110 mV) and E = -0.92 V (ΔEp = 120 mV)) responses. Upon oxidation using a stoichiometric amount of [FeIII(η5-C5H5)2](PF6), 1·CH2Cl2 yielded [Cu(L1)2](PF6) (2). Structural analysis (100 K) reveals that 1·CH2Cl2 is a fou…

Six-coordinate [CoIII(L)2]z (z = 1−, 0, 1+) complexes of an azo-appended o-aminophenolate in amidate(2−) and iminosemiquinonate π-radical (1−) redox-levels: the existence of valence-tautomerism

Aerobic reaction of the ligand H2L1, 2-(2-phenylazo)-anilino-4,6-di-tert-butylphenol, CoCl2·6H2O and Et3N in MeOH under refluxing conditions produces, after work-up and recrystallization, black crystals of [Co(L1)2] (1). When examined by cyclic voltammetry, 1 displays in CH2Cl2 three one-electron redox responses: two oxidative, E11/2 = 0.30 V (peak-to-peak separation, ΔEp = 100 mV) and E21/2 = 1.04 V (ΔEp = 120 mV), and one reductive E1/2 = −0.27 V (ΔEp = 120 mV) vs. SCE. Consequently, 1 is chemically oxidized by 1 equiv. of [FeIII(η5-C5H5)2][PF6], affording the isolation of deep purple crystals of [Co(L1)2][PF6]·2CH2Cl2 (2), and one-electron reduction with [CoII(η5-C5H5)2] yielded bluish-b…

Diphenoxido‐Bridged Co II and Zn II Complexes of Tripodal N 2 O 2 Ligands: Stabilisation of M II ‐Coordinated Phenoxyl Radical Species

Three new tripodal ligands with an N 2 O 2 donor set, namely 2-tert-butyl-6-({(2-hydroxybenzyl)[2-(2-pyridyl)ethyl]amino}-methyl)-4-methylphenol (H 2 L 1 ), 2-tert-butyl-6-({(2-hydroxybenzyl)[2-(2-pyridyl)ethyl]amino}methyl)-4-methoxy-phenol (H 2 L 2 ) and 2-tert-butyl-6-({[2-(dimethylamino)ethyl]-(2-hydroxybenzyl)amino}methyl)-4-methoxyphenol (H 2 L 3 ) have been synthesised. Treatment of the ligands with Co-(CH 3 CO 2 ) 2 ·4H 2 O or [Zn(H 2 O) 6 ][ClO 4 ] 2 in the presence of Et 3 N provides the corresponding Co II and Zn" complexes of composition [M II 2 (L 1 ) 2 ] [M = Co (1) (single-crystals are a solvate with the composition [Co II 2 (L 1 ) 2 ]·2CHCl 3 , i.e. 1·2CHCl 3 ); M = Zn (2)],…

Coordination versatility of 1,3-bis[3-(2-pyridyl)pyrazol-1-yl]propane: Co(II) and Ni(II) complexes

Abstract The ligand 1,3-bis[3-(2-pyridyl)pyrazol-1-yl]propane (L8) has afforded six-coordinate monomeric and dimeric complexes [(L8)CoII(H2O)2][ClO4]2 (1), [(L8)NiII(MeCN)2][BPh4]2 (2), [(L8)NiII(O2CMe)][BPh4] (3), and [ ( L 8 ) 2 Co 2 II ( μ - O 2 CMe ) 2 ] [ BPh 4 ] 2 ( 4 ) . The crystal structures of 1, 2 · MeCN, 3, and 4 revealed that the ligand L8 is flexible enough to expand its coordinating ability by fine-tuning the angle between the chelating fragments and hence folds around cobalt(II)/nickel(II) centers to act as a tetradentate chelate, allowing additional coordination by two trans-H2O, cis-MeCN, and a bidentate acetate affording examples of distorted octahedral Co II N 2 ( pyridy…

Modeling Tyrosinase and Catecholase Activity Using New m-Xylyl-Based Ligands with Bidentate Alkylamine Terminal Coordination

Chemical model systems possessing the reactivity aspects of both tyrosinase and catechol oxidase are presented. Using two m-xylyl-based ligands providing bidentate alkylamine terminal coordination, 1,3-bis[(N,N-dimethylaminoethyl)aminomethyl]benzene (L(H,H)) and 1,3-bis[(N,N,N'-trimethylaminoethyl)aminomethyl]benzene (L(Me,Me)), four new dicopper(I) complexes, [Cu(I)(2)(L(H,H))(MeCN)(4)][ClO(4)](2) (1), [Cu(I)(2)(L(H,H))(PPh(3))(2)(MeCN)(2)][ClO(4)](2) (2), [Cu(I)(2)(L(Me,Me))(MeCN)(2)][ClO(4)](2) (3), and [Cu(I)(2)(L(Me,Me))(PPh(3))(2)][ClO(4)](2) (4), have been synthesized and characterized. Complex 2 has been structurally characterized. Reaction of the dicopper(I) complex 3(2+) with diox…

A phenoxo-bridged dicopper(ii) complex as a model for phosphatase activity: mechanistic insights from a combined experimental and computational study

A μ-phenoxo-bis(μ2-1,3-acetato)-bridged dicopper(II) complex [CuII2(L1)(μ-O2CMe)2][NO3] (1) has been synthesized from the perspective of modeling phosphodiesterase activity. Structural characterization was done initially with 1·3Et2O (vapour diffusion of Et2O into MeOH solution of 1; poor crystal quality) and finally with its perchlorate salt [CuII2(L1)(μ-O2CMe)2][ClO4]·1.375MeCN·0.25H2O, crystallized from vapour diffusion of n-pentane into a MeCN–MeOH mixture (comparatively better crystal quality). An asymmetric unit of such a crystal contains two independent molecules of compositions [CuII2(L1)(μ-O2CMe)2][ClO4] and [CuII2(L1)(μ-O2CMe)2(MeCN)][ClO4] (coordinated MeCN with 0.75 occupancy), …

Nickel(II) Complex of a Hexadentate Ligand with Two o-Iminosemiquinonato(1-) π-Radical Units and Its Monocation and Dication.

Aerobic reaction of a hexadentate redox-active o-aminophenol-based ligand, H4L(3) = N,N'-bis(2-hydroxy-3,5-di-tert-butylphenyl)-2,2'-diamino(diphenyldithio)-ethane, in CH3OH with Ni(II)(O2CCH3)2·4H2O and Et3N afforded isolation of a reddish-brown crystalline solid [Ni(L(3))] 1. Cyclic voltammetry (CV) experiment exhibits two oxidative responses at E1/2 = 0.09 and 0.53 V vs SCE (saturated calomel electrode). Chemical oxidation of 1 in air by [Fe(III)(η(5)-C5H5)2][PF6] and AgBF4 in CH2Cl2 led to the isolation of one-electron oxidized species [1](1+) as purple [1][PF6]·CH2Cl2 and two-electron oxidized species [1](2+) as dark purple [1][BF4]2·CH2Cl2, respectively. X-ray crystallographic analysi…

Six-coordinate CoIII and four-coordinate MII (M = Co, Zn) mixed-valence dimers supported by a deprotonated pyridine amide ligand: magnetism of a CoIIICoII complex and C–H⋯O/Cl/Br interactions

Using a pyridine amide ligand 4-methyl-2-{N-(2-pyridyl)carbamoyl}pyridine (HL), in its deprotonated form, binuclear mixed-valence homonuclear bimetallic complexes [CoIII,II2(L)3(X)]X·S [X = Cl (1); X = Br, S = CH3OH (2)] and heteronuclear bimetallic complex [CoIIIZnII(L)3(Cl)]Cl·CH3OH·5H2O (3) have been synthesized. Structural analysis revealed that trivalent cobalt is in distorted octahedral and bivalent cobalt/zinc is in distorted tetrahedral environment. Three L(−) ligands provide six-coordination by utilizing three pyridine amide units (pyridine N and amide N donor set) in a facial mode, which in turn places three 4-methylpyridine nitrogens to coordinate to another metal center, which c…

Mono- and Di-chloro-bridged Discrete Dimers and Trimers and Mono-Chloro-Bridged 1D-Coordination Polymer of Copper(II). Magneto-structural Studies

The synthesis, structural characterization, and magnetic properties of three copper(II) complexes, a mono-chloro-bridged [Cu2II(L6)2(μ-Cl)(Cl)(CuIICl4)] (1) and a dichloro-bridged [CuII2(L7)2(μ-Cl)2][ClO4]2 (3) discrete trimers and dimers, and a mono-chloro-bridged 1D-coordination polymer [CuII(L6)(μ-Cl)][ClO4]·CH3CN (2), are reported. Molecular structures were authenticated by X-ray crystallography. Temperature-dependent magnetic measurements carried out on powdered samples of 1–3 indicated a very weak antiferromagnetic exchange-coupling within the {CuII(μ-Cl)CuII(μ-Cl)CuIICl3}+ units in 1 [Curie-Weiss plot: θ = –0.19(1) K and g = 2.07(1)], a ferromagnetic behavior within {CuII(μ-Cl)2CuII}…

One‐Dimensional Coordination Polymers of Mn II , Cu II , and Zn II Supported by Carboxylate‐Appended (2‐Pyridyl)alkylamine Ligands – Structure and Magnetism

Four new complexes [MnII(L1OO)(H2O)][ClO4]·2H2O (1), [ZnII(L1OO)][ClO4]·2H2O (2), [CuII(L3OO)][CF3SO3]·H2O (3), and [ZnII(L3OO)][ClO4] (4) (L1OO– = 3-[(2-(pyridine-2-yl)ethyl){2-(pyridine-2-yl)methyl}amino]propionate; L3OO– = 3-[(2-(pyridine-2-yl)ethyl){(dimethylamino)ethyl}amino]propionate) have been synthesized and characterized by elemental analysis, IR, and UV/Vis spectroscopy. Structural analysis revealed that 1, 3, and 4 are one-dimensional chain-like coordination polymers. In 1 distorted octahedral MnN3O3 and in 3 square-pyramidal CuN3O2 coordination is satisfied by three nitrogen atoms and an appended carboxylate oxygen atom of the ligand, and an oxygen atom belonging to the carboxy…

Isostructural Dinuclear Phenoxo-/Acetato-Bridged Manganese(II), Cobalt(II), and Zinc(II) Complexes with Labile Sites: Kinetics of Transesterification of 2-Hydroxypropyl-p-nitrophenylphosphate

Using the dinucleating phenol-based ligand 2,6-bis[3-(pyridin-2-yl)pyrazol-1-ylmethyl]-4-methylphenol] (HL(2)), in its deprotonated form, the six new dinuclear complexes [M(II)(2)(L(2))(μ-O(2)CMe)(2)(MeCN)(2)][PF(6)] (M = Mn (2a), Co (3a), Zn (4a)) and [M(II)(2)(L(2))(μ-O(2)CMe)(2)(MeCN)(2)][BPh(4)] (M = Mn (2b), Co (3b), Zn (4b)) have been synthesized. Crystallographic analyses on 2b·2MeCN, 3b·2MeCN, and 4b·2MeCN reveal that these complexes have closely similar μ-phenoxo bis(μ-carboxylato) structures. The physicochemical properties (absorption and ESI-MS spectral data, 2a,b, 3a,b, and 4a,b; (1)H NMR, 4a,b) of the cations of 2a-4a are identical with those of 2b-4b. Each metal ion is termina…

Dimeric Mn(ii), Co(ii), Ni(ii) and Cu(ii) complexes of a common carboxylate-appended (2-pyridyl)alkylamine ligand: structure, magnetism and DFT study

Four new complexes of composition [MII2(L3)2(CH3OH)2](ClO4)2 (M = Mn, 1; Co, 2; Ni, 3) and [CuII2(L3)2](ClO4)2 (4) (L3(−) = 3-[2-(((6-methyl)pyridin-2-yl)methyl){(dimethylamino)ethyl}-amino]propionate) have been synthesized and characterized. Structural analysis reveals that 1–4 are discrete syn–anti carboxylate-bridged binuclear coordination complexes with a {MII2(–O–C–O–)2}2+ structural motif. In 1–3 distorted octahedral MN3O3 and in 4 distorted square pyramidal CuN3O2 coordination is satisfied at each M(II) center by three N (a pyridyl and two tertiary aliphatic amines) and a carboxylate O of the ligand, and an O of the carboxylate group. In 1–3 the M(II) center is also coordinated by a …

Syntheses, X-ray structures, and physicochemical properties of phenoxo-bridged dinuclear nickel(II) complexes: kinetics of transesterification of 2-hydroxypropyl-p-nitrophenylphosphate.

Four dinuclear nickel(II) complexes [Ni(II)(2)(L(1))(O(2)CMe)(2)(H(2)O)(2)][PF(6)].MeOH.3H(2)O (1), [Ni(II)(2)(L(1))(O(2)CMe)(2)(NCS)] (2), [Ni(II)(2)(L(2))(O(2)CMe)(2)(MeOH)(H(2)O)][ClO(4)] (3), and [Ni(II)(2)(L(2))(O(2)CMe)(2)(MeOH)(H(2)O)][BPh(4)].3MeOH.H(2)O (4) have been synthesized [HL(1): 2,6-bis[N-methyl-N-(2-pyridylethyl)amino]-4-methylphenol; HL(2): 2,6-bis[3-(pyridin-2-yl)pyrazol-1-ylmethyl]-4-methylphenol]. Complexes 1, 3, and 4 are new while complex 2 was reported previously by Fenton and co-workers (the structure of 2 was presented but no physicochemical properties of this complex were reported; in this work such studies have been completed). X-ray crystallographic analyses of…

Unprecedented heptacopper(ii) cluster with body-centred anti-prismatic topology. Structure, magnetism and density functional study

Using a (2-pyridyl)ethylamine-appended carboxylate ligand a new cluster [Cu(II)(7)(L)(4)(μ(3)-OH)(2)(H(2)O)(2)(DMF)(2)][ClO(4)](4)·4H(2)O (1) [L(2-): N-{CH(2)CH(2)(2-pyridyl)}(CH(2)CH(2)CO(2))(2)] is synthesized, as a result of 'coordination-driven self-assembly'. The structure of 1 is unique and consists of a centrosymmetric carboxylato- and hydroxo-bridged heptanuclear copper(II) cation, with body-centred anti-prismatic topology. The four crystallographically independent copper(II) centres differ markedly in their coordination geometry. In addition to establishing cluster authenticity, the structural analysis of 1 discloses two notable features. The existence of {Cu(II)(3)(μ(3)-OH)}(5+) c…

Phenolate- and acetate (both μ2-1,1 and μ2-1,3 modes)-bridged linear Co(II)3 and Co(II)2Mn(II) trimers: magnetostructural studies.

A full report on the synthesis, crystal structure, spectroscopic characterization, and magnetic properties of two new trinuclear complexes (one homo- and another heterotrinuclear) [(L)2Co(II)3(OAc)4(MeOH)2]·6MeOH (1) and [(L)2Co(II)2Mn(II)(OAc)4(MeOH)2]·6MeOH (2) [HL = N-methyl-N-2-hydroxybenzyl-2-aminoethyl-2-pyridine] is presented. The properties of 1 and 2 are compared to that of three previously communicated complexes [(L)2Ni(II)3(OAc)4(MeOH)2]·6MeOH (3), [(L)2Ni(II)2Mn(II)(OAc)4(H2O)2] (4), and [(L)2Ni(II)2Co(II)(OAc)4(MeOH)2]·6MeOH (5) (Inorg. Chem.2007, 46, 5128-5130). All are centrosymmetric trimers with the central metal ion situated on an inversion center. Adjacent metal ions are …

Molecular squares of Ni(II) and Cu(II): ferromagnetic exchange interaction mediated by syn-anti carboxylate-bridging.

The synthesis of four discrete tetranuclear complexes {[Ni(II)(L(2))][ClO(4)]}(4).MeCN (1), {[Cu(II)(L(1))(O(3)SCF(3))]}(4).H(2)O (), {[Cu(II)(L(3))(OClO(3))]}(4).MeCN () and {[Cu(II)(L(4))][ClO(4)]}(4).3MeCN.4H(2)O (4), supported by a closely similar group of carboxylate-appended (2-pyridyl)alkylamine ligands [L(1)(-): 3-[N-methyl-{2-(pyridin-2-yl)ethyl}amino]propionate; L(2)(-): 3-[(2-(pyridin-2-yl)ethyl){2-(pyridin-2-yl)methyl}amino]propionate; L(3)(-): 3-[N-isopropyl-{2-(pyridin-2-yl)methyl}amino]propionate and L(4)(2-): 3-[N-{2-(pyridin-2-yl)methyl}amino]-bis(propionate)] is described. Structural characterization reveals that each Ni(II) centre in 1 has square-pyramidal Ni(II)N(3)O(2) …

A Bioinspired Dinickel(II) Hydrolase: Solvent Vapor-Induced Hydrolysis of Carboxyesters under Ambient Conditions

From the perspective of synthetic metallohydrolases, a phenoxo-bridged dinickel(II) complex [NiII2(L)(H2O)2(CH3OH)][ClO4]·CH3OH (1) (H3L = 2,6-bis[{{(5-bromo-2-hydroxybenzyl)(N′,N″-(dimethylamino)ethyl)}amino}methyl]-4-methylphenol) has been synthesized and structurally characterized. The presence of a vacant coordination site and a weakly bound water molecule provides the scope for substrate binding to act as a metallohydrolase model. Ethyl acetate vapor diffusion at 298 K to a CH3CN/CH3OH solution of 1 results in the formation of a pentanuclear acetato-bridged complex [NiII5(H2L)2(μ3-OH)2(μ-O2CCH3)4][ClO4]2·CH3CO2C2H5 (2), demonstrating for the first time the metal-coordinated water-promo…

Bis‐μ‐pyrazolate‐Bridged Dinickel(II) and Dicopper(II) Complexes: An Example of Stereoelectronic Preference of Metal Ions and Stabilization of Mixed‐Valence Ni III Ni II Species

New dimeric nickel(II) and copper(II) complexes [(L)Ni(μ-L′)]2[ClO4]21 and [(L)Cu(μ-L′)]2[ClO4]22, [2-[3-(2′-pyridyl)pyrazol-1-ylmethyl]pyridine (L) and 3-(2-pyridyl)pyrazole (HL′)] have been synthesized, structurally characterized, and their absorption, magnetic, EPR and redox properties investigated. The crystal structure of 1·MeCN reveals a planar {Ni2(μ-L′)2}2+ core [Ni···Ni separation: 4.0765(10) A] in which each distorted octahedral NiII ions is terminally coordinated by a tridentate ligand L and bridged by two HL′ units, in their deprotonated form. The structural analysis of 2·2MeCN reveals two five-coordinate CuII ions, each terminally coordinated by adopting only a bidentate coordi…

A carboxylate-bridged NiII8 cluster with a distorted cubane topology: structure, magnetism and density functional studies

Using a dicarboxylate ligand appended with (2-pyridyl)ethylamine unit, a new cluster [NiII8(L4)6(DMF)2(CH3OH)2(H2O)6][ClO4]4·2CH3OH·2CH3CO2C2H5 (1) [L4(2−): 3-[N-{2-(pyridin-2-yl)ethyl}amino]-bis(propionate)] has been synthesized, through ‘coordination-driven self-assembly’. The crystal structure of 1 reveals a centrosymmetric octanuclear carboxylate-bridged nickel(II) tetracation, with a distorted cubane topology. The four crystallographically independent nickel(II) centres differ markedly in their coordination environment. Magnetic studies (2–300 K) reveal that in 1 the net magnetic-exchange is antiferromagnetic. Based on geometric parameters associated with two interacting nickel(II) cen…

Chemical Fixation of Atmospheric CO2 by Copper(II) Complexes of a Tridentate N -donor Ligand