Spectroscopic approach in characterization of chromium(III), manganese(II), iron(III) and copper(II) complexes with a nitrogen donor tetradentate, 14-membered azamacrocyclic ligand

The complexes of Cr(III), Mn(II), Fe(III) and Cu(II) were synthesized with the macrocyclic ligand i.e. 2,3,9,10-tetraketo-1,4,8,11-tetraazacyclotetradecane. The ligand was prepared by the [2 + 2] condensation reaction of diethyloxalate and 1,3-diamino propane. These complexes were found to have the general composition M(L)X3 and M'(L)X2 [where M = Mn(II) and Cu(II), M' = Cr(III) and Fe(III), L = ligand (N4) and X = Cl-, NO3-, 1/2SO4(2-) and [CH3COO-]. The ligand and its transition metal complexes were characterized by the elemental analyses, molar conductance, magnetic susceptibility, mass, IR, electronic, and EPR spectral studies. On the basis of IR, electronic and EPR spectral studies an octahedral geometry has been assigned for Cr(III), Mn(II) and Fe(III) and a tetragonal geometry for Cu(II) complexes.     

Hydrogen chemical ionization mass spectrometry of metalloporphyrins

The hydrogen chemical ionization (H₂ CI) mass spectra of a range of metal(II) (Ni, Cu, Co, Pt), metal (III) (Al, Mn, Ga, Fe (bearing a single axial ligand)) and metal(IV) (Si, Ge, Sn (bearing two axial ligands) and V (as V?O²⁺)) porphyrins have been determined, The spectra are highly dependent on the coordinated metal, rather than the axial ligand(s) (where present). Ni(II), Cu(II), Mn(II or III), Ga(III), Ge(IV), Fe(III) and Sn(IV) porphyrins fragment via hydrogenation and demetallation, followed by cleavage of the resulting porphyrinogens at the meso(bridge) positions to give mono- and di-pyrrolic fragments. Tripyrrolic fragments are also observed in the case of Ni(II), Cu(II) and Sn(IV). Fragmentations of this type are similar to those observed for free-base porphyrins. In the case of Pt(II), Co(II), Al(III), Si(IV) and V(IV) (as vanadyl), the dipyrrolic fragment ions are either very weak or completely absent; hence their H₂CI spectra contain limited structural information. This variable CI behaviour may be related to the relative stabilities of the metalloporphyrins together with the multiple stable valency states exhibited by several metals.     

Synthesis and spectral studies of transition metal complexes with 1,5:11,15-dimetheno-2,4,10,12-tetramethyl-[1,5,9,13]-tetraazahexadeca-1,3,5,6,10,11,13,15,16,20-decene a sixteen-membered tetradentate macrocyclic ligand

Complexes of Cr(III), Mn(II), Fe(III), Co(II), Ni(II), Cu(II), Pd(II), Pt(II), Ru(III) and Ir(III) with a sixteen-membered 1,5:11,15-dimetheno-2,4,10,12-tetramethyl-[1,5,9,13]-tetraazahexadeca-1,3,5,6,10,11,13,15,16,20-decene macrocyclic ligand have been synthesized. These complexes are characterized by magnetic moment, infrared, electronic, EPR and mössbauer spectral studies. All of complexes were found to have six-coordinated octahedral geometry and are of the high spin type except for the Pd(II) and Pt(II) complexes which are four coordinate, square planar and diamagnetic.     

Phenoxo-bridged symmetrical homobinuclear complexes derived from an “end-off” compartmental ligand, 2,6- bis [5′-chloro-3′-phenyl- 1H -indole-2′-carboxamidyliminomethyl]-4-methylphenol

A compartment ligand 2,6-bis[5′-chloro-3′-phenyl-1H-indole-2′-carboxamidyliminomethyl]-4-methylphenol was prepared and homobinuclear phenol-bridged Cu(II), Ni(II), Co(II), Zn(II), Cd(II), Hg(II), Fe(III), and Mn(II) complexes have been prepared by the template method using the precursors 2,6-diformyl-4-methylphenol, 5-chloro-3-phenylindole-2-carbohydrazide and metal chlorides in 1 : 2 : 2 ratio, respectively. The complexes were characterized by elemental analyses, conductivity measurements, magnetic susceptibility data, IR, NMR, FAB mass and ESR spectra, TGA, and powder XRD data. Cu(II), Co(II), Zn(II), Cd(II) and Hg(II) complexes exhibit square pyramidal geometry whereas Ni(II), Mn(II), and Fe(III) complexes are octahedral. Low magnetic moment values for Cu(II), Ni(II), Co(II), Fe(III), and Mn(II) complexes show antiferromagnetic spin-exchange interaction between two metal centers in binuclear complexes. The ligand and its complexes were tested for antibacterial activity against Escherichia coli and Staphyloccocus aureus, and antifungal activity against Aspergillus niger and Candida albicans.     

Catalytic Activity of 3d-Metal Coordination Compounds with Diphenylthiocarbazide

The catalytic activity of Cr(III), Mn(II), Fe(III), Co(II), Ni(II), and Cu(II) diphenylthiocarbazide complexes in decomposition of hydrogen peroxide was studied. The activation energies of this reaction were correlated with the strength of ligand bonding to the metal atom in the catalyst molecule.     

Complexation and Thermal Studies of Uric Acid with Some Divalent and Trivalent Metal Ions of Biological Interest in the Solid State

Nine new [metal uric acid] complexes [M(Ua) n ]°·XH 2 O have been synthesized. These complexes have been characterized by elemental analysis, X-ray diffraction (XRD), magnetic susceptibility ( w eff. ), FTIR spectra, thermal analysis (TG & DTA), and electronic spectra (UV/visible). Uric acid (HUa) coordinates as a bidentate ligand to Mn(II), Fe(II), Co(II), Ni(II), Cu(II), Zn(II), Al(III), Cr(III) and Fe(III) through the protonated N-7 within the imidazole ring and O-6 within the pyrimidine ring. Uric acid forms neutral metal urate complexes with all the above metal ions. The quantitative compositions were determined as [M(Ua) 2 ·(H 2 O) 2 ]°·XH 2 O where M(II)=Mn, Fe, Co, Ni, Cu, Zn and X=2, 4, 2, 4, 2, 2, respectively. The M(II) complexes exhibit an isostructural octahedral coordination with N-7, O-6 of two uric acid ligand molecules, and O of two water molecules. Compositions were also determined as [M(Ua) 3 ]°·YH 2 O where M(III)=Al, Cr, Fe and Y=6, 3, 3 respectively. All the M(III) complexes form an isostructural octahedral coordination with N-7 and O-6 of three uric acid ligand molecules. Iron(III) complexes prepared with N 1 , N 3 and N 9 -methyl uric acid yielded brown complexes with a metal ligand ratio of 1 3, while N 7 -methyl uric acid did not yield a complex due to blockage of N-7 with a methyl group.     

Synthesis, spectroscopic and thermal studies of transition metal complexes derived from benzil and diethylenetriamine

A macrocyclic ligand, bdta (where bdta=3,6,9,12,15,18-hexaaza-1,2,10,11-tetraphenyl-2,9,11,18-tetraenecyclododecane) has been prepared by cyclocondensation of benzil with diethylenetriamine which efficiently encapsulates transition as well as pseudo-transition metal ions leading to the formation of M(bdta)Cl2 type complexes [where M=Mn(II), Fe(II), Co(II), Ni(II), Cu(II), Zn(II), Cd(II) and Hg(II)]. The analytical, spectroscopic and magnetic moment data suggests an octahedral geometry for all the complexes. EPR spectra of Mn(II) and Cu(II) show considerable exchange interaction in the complex. They are non-conducting in DMSO. The TGA profile of the ligand and its complexes are identical and consists of two discreet stages. The voltammogram of Cu-complex exhibits a quasi-reversible one-electron transfer wave for Cu(II)/Cu(I) couple.     

Preparation and characterization of Cr(III), Mn(II), Fe(II), Co(II) and Ni(II) complexes of a hexaazadithiophenolate macrocycle

The ligating properties of the 24-membered macrocyclic dinucleating hexaazadithiophenolate ligand (L(Me))2- towards the transition metal ions Cr(II), Mn(II), Fe(II), Co(II), Ni(II) and Zn(II) have been examined. It is demonstrated that this ligand forms an isostructural series of bioctahedral [(L(Me))M(II)2(OAc)]+ complexes with Mn(II) (2), Fe(II) (3), Co(II) (4), Ni(II) (5) and Zn(II) (6). The reaction of (L(Me))2- with two equivalents of CrCl2 and NaOAc followed by air-oxidation produced the complex [(L(Me))Cr(III)H2(OAc)]2+ (1), which is the first example for a mononuclear complex of (L(Me))2-. Complexes 2-6 contain a central N3M(II)(mu-SR)2(mu-OAc)M(II)N3 core with an exogenous acetate bridge. The Cr(III) ion in is bonded to three N and two S atoms of (L(Me))2- and an O atom of a monodentate acetate coligand. In 2-6 there is a consistent decrease in the deviations of the bond angles from the ideal octahedral values such that the coordination polyhedra in the dinickel complex 5 are more regular than in the dimanganese compound 2. The temperature dependent magnetic susceptibility measurements reveal the magnetic exchange interactions in the [(L(Me))M(II)2(OAc)]+ cations to be relatively weak. Intramolecular antiferromagnetic exchange interactions are present in the Mn(II)2, Fe(II)2 and Co(II)2 complexes where J = -5.1, -10.6 and approximately -2.0 cm(-1) (H = -2JS1S2). In contrast, in the dinickel complex 5 a ferromagnetic exchange interaction is present with J = +6.4 cm(-1). An explanation for this difference is qualitatively discussed in terms of the bonding differences.     

Catalytic asymmetric cyclopropanation at a chiral platform

Novel chiral Robson-type macrocyclic complexes M(2)-L [where M = Mn(II), Mn(III), Co(II) and Co(III) and L denotes tetra-Schiff base chiral ligands, L1 or L2] have been synthesized by metal template condensation of 2,6-diformyl-4-methyl-phenol, with 1R,2R-diaminocyclohexane (L1) or 1R,2R-diphenylethylenediamine (L2). The dinuclear Co(II) and Co(III) complexes catalyze asymmetric cyclopropanation of styrene with diazoacetate cooperatively and with high enantioselectivity.     

A geometrically constraining bis(benzimidazole) ligand and its nearly tetrahedral complexes with Fe(II) and Mn(II)

2,2'-Bis[2-(1-propylbenzimidazol-2-yl)]biphenyl), 4, and its bis complexes with Fe(II) and Mn(II) have been prepared and characterized structurally and spectroscopically. Ligand 4 adopts an open, "trans" conformation in the solid state with the benzimidazole (BzIm) groups on opposite sides of the biphenyl unit. In its complexes with metal ions, a "cis" conformation is observed, and 4 behaves as a geometrically constraining bidentate ligand with four planar groups connected by three "hinges". Reaction of 4 with Fe(II) or Mn(II) yielded isomorphous crystals (space group Pnn2) of Fe(II)(4)2.(ClO4)2 and Mn(II)(4)2.(ClO4)2, in which the M(II)(4)2 cations exhibit distorted-tetrahedral coordination geometries (N-M-N angles, 109 +/- 11 degrees ) enforced by rigid, chiral nine-membered M(4) rings in the twist-boat-boat conformation. Individually, the cations show R,R or S,S stereochemistry, and the crystals are racemates. Mn(II)(4)2.(ClO4)2 exhibits a quasi-reversible Mn(II) --> Mn(III) oxidation at E(1/2) = 0.64 V; the corresponding Fe(II) --> Fe(III) oxidation occurs at E(1/2) = 1.76 V. The electrochemical stability of the Fe(III) oxidation state in this system suggests the possibility of isolating an unusual pseudotetrahedral Fe(III)N(BzIm)(4) species. Ultraviolet spectra of the iron and manganese complexes are dominated by absorptions of the ligand 4 blue-shifted by approximately 2000-3000 cm(-1). Ligand-field absorptions were observed for the Fe(II) complex; those for the Mn(II) complex were obscured by tailing ultraviolet absorptions. Electron paramagnetic resonance and magnetic susceptibility measurements are consistent with a high-spin Mn(II) complex, while for the Fe(II) complex, the falloff of the magnetic moment with decreasing temperature is indicative of zero-field splitting with D approximately 4 cm(-1).     

Spectroscopic characterization and EPR spectral studies on transition metal complexes with a novel tetradentate, 12-membered macrocyclic ligand

Complexes of Cr(III), Mn(II), Co(II), Ni(II) and Cu(II) containing a tetradentate macrocyclic N-donor ligand have been prepared via template reaction of 2,3-pentanedione, ethylene-di-ammine and transition metal ions. The complexes have been characterized on the basis of the elemental analysis, molar conductance, magnetic moment susceptibility, IR, electronic and EPR spectral studies. The complexes are of high spin type and possess four coordinate tetrahedral five coordinate square pyramidal and six coordinated octahedral/tetragonal geometry.     

Synthesis, characterization and biological activities of Cu(II), Co(II), Mn(II), Fe(II), and UO2(VI) complexes with a new Schiff Base hydrazone: O-hydroxyacetophenone-7-chloro-4-quinoline hydrazone

The Schiff base hydrazone ligand HL was prepared by the condensation reaction of 7-chloro-4-quinoline with o-hydroxyacetophenone. The ligand behaves either as monobasic bidentate or dibasic tridentate and contain ONN coordination sites. This was accounted for be the presence in the ligand of a phenolic azomethine and imine groups. It reacts with Cu(II), Ni(II), Co(II), Mn(II), UO(2) (VI) and Fe(II) to form either mono- or binuclear complexes. The ligand and its metal complexes were characterized by elemental analyses, IR, NMR, Mass, and UV-Visible spectra. The magnetic moments and electrical conductance of the complexes were also determined. The Co(II), Ni(II) and UO(2) (VI) complexes are mononuclear and coordinated to NO sites of two ligand molecules. The Cu(II) complex has a square-planar geometry distorted towards tetrahedral, the Ni(II) complex is octahedral while the UO(2) (VI) complex has its favoured heptacoordination. The Co(II), Mn(II) complexes and also other Ni(II) and Fe(III) complexes, which were obtained in the presence of Li(OH) as deprotonating agent, are binuclear and coordinated via the NNNO sites of two ligand molecules. All the binuclear complexes have octahedral geometries and their magnetic moments are quite low compared to the calculated value for two metal ions complexes and thus antiferromagnetic interactions between the two adjacent metal ions. The ligand HL and metal complexes were tested against a strain of Gram +ve bacteria (Staphylococcus aureus), Gram -ve bacteria (Escherichia coli), and fungi (Candida albicans). The tested compounds exhibited high antibacterial activities.     

Studies on catalytic fluorescence formation with peroxidase-like metallotetrakis(N-methylpyridiniumyl) porphyrins

The relative ability of peroxidase-like metallotetrakis(N-methylpyridiniumyl)porphyrins [Me-TMPyP, Me = Mn(III), Fe(III), Co(III), Ni(II), Cu(II), and Zn(II)] to catalyse the hydrogen peroxide oxidation of homovanillic acid to a fluorescent dimer has been studied. The complexes of Mn, Fe and Co are effective catalysts in the reaction, but the complexes of Ni, Cu and Zn are not. The catalytic behaviour of Mn-TMPyP, Fe-TMPyP and Co-TMPyP has been compared with that of HRP in both enzymatic and kinetic analysis. The sequence of peroxidase-like catalytic activity is Mn-TMPyP> Co-TMPyP> Fe-TMPyP. The catalytic activity of Mn-TMPyP is 84% of that of HRP. These Me-TMPyP (Me = Mn, Fe, and Co) compounds are good substitutes for HRP in enzymatic analysis. Traces of hydrogen peroxide and glucose can be determined with the Me-TMPyP systems.     

Potential of ethylenediaminedi(o-hydroxyphenylacetic acid) and N,N'-bis(hydroxybenzyl)ethylenediamine-N,N'-diacetic acid for the determination of metal ions by capillary electrophoresis

Two aromatic polyaminocarboxylate ligands, ethylenediaminedi(o-hydroxyphenylacetic acid) (EDDHA) and N,N′-bis(hydroxybenzyl)ethylenediamine-N,N′-diacetic acid (HBED), were applied for the separation of transition and heavy metal ions by the ion-exchange variant of electrokinetic chromatography. EDDHA structure contains two chiral carbon centers. It makes it impossible to use the commercially available ligand. All the studied metal ions showed two peaks, which correspond to meso and rac forms of the ligand. The separation of metal–HBED chelates was performed using poly(diallyldimethylammonium) polycations in mixed acetate–hydroxide form. Simultaneous separation of nine single- and nine double-charged HBED chelates, including In(III), Ga(III), Co(II)–(III) and Mn(II)–(III) pairs demonstrated the efficiency of 40 000–400 000 theoretical plates. The separation of Co(III), Fe(III) complexes with different arrangements of donor groups and oxidation of Co(II), Mn(II), Fe(II) ions in reaction with HBED have been discussed.     

Nine non-symmetric pyrazine-pyridine imide-based complexes: reversible redox and isolation of [M(II/III)(pypzca)2](0/+) when M = Co, Fe

The non-symmetric imide ligand Hpypzca (N-(2-pyrazylcarbonyl)-2-pyridinecarboxamide) has been deliberately synthesised and used to produce nine first row transition metal complexes: [M(II)(pypzca)(2)], M = Zn, Cu, Ni, Co, Fe; [M(III)(pypzca)(2)]Y, M = Co and Y = BF(4), M = Fe and Y = ClO(4); [Cu(II)(pypzca)(H(2)O)(2)]BF(4), [Mn(II)(pypzca)(Cl)(2)]HNEt(3). These are the first deliberately prepared complexes of a non-symmetric imide ligand. X-ray crystal structures of [Cu(II)(pypzca)(2)]·H(2)O, [Co(II)(pypzca)(2)], [Co(III)(pypzca)(2)]BF(4), [Cu(II)(pypzca)(H(2)O)(2)]BF(4)·H(2)O and [Mn(II)(pypzca)Cl(2)]HNEt(3) show that each of the (pypzca)(-) ligands binds in a meridional fashion via the N(3) donors. In the first three complexes, two such ligands are bound such that the 'spare' pyrazine nitrogen atoms are positioned approximately orthogonally to one another and also to the imide oxygen atoms. In MeCN the [M(II/III)(pypzca)(2)](0/+) complexes, where M = Ni, Co or Fe, exhibit one reversible metal based M(II/III) process and two distinct, quasi-reversible ligand based reduction processes, the latter also observed for M(II) = Zn. [Mn(II)(pypzca)Cl(2)]HNEt(3) displays a quasi-reversible oxidation process in MeCN, along with several irreversible processes. Both copper(II) complexes show only irreversible processes. Variable temperature magnetic measurements show that [Fe(III)(pypzca)(2)]ClO(4) undergoes a gradual spin crossover from partially high spin at 298 K (3.00 BM) to fully low spin at 2 K (1.96 BM), and that [Co(II)(pypzca)(2)] remains high spin from 298 to 4 K. All of the complexes are weakly coloured, other than [Fe(II)(pypzca)(2)] which is dark purple and absorbs strongly in the visible region.     

Sorption of transition metals by silica gel with fixed amide of maleic acid and polyhexamethyleneguanidine on the surface

The possibility was determined for covalent binding of amide of maleic acid and polyhexamethyleneguanidine to a silica gel surface previously activated with cyanur chloride. Adsorption of Zn(II), Cd(II), Pb(II), Cu(II), Mn(II), Ni(II), Fe(III), and Co(II) cations from aqueous solution with a modified silica obtained was studied. The possibility of subsequent formation on the surface of mixed ligand complexes     

Iron(II) complexes with amide-containing macrocycles as non-heme porphyrin analogues

Iron(II) complexes of macrocyclic pentadendate ligands 3,6,9,12,18-pentaazabicyclo[12.3.1]octadeca-1(18),14,16-triene-2,13-dione (H2pydioneN5) and 16-chloro-3,6,9,12,18-pentaazabicyclo[12.3.1]octadeca-1(18),14,16-triene-2,13-dione (H2pyCldioneN5) were synthesized and fully characterized. Complexes with one or two deprotonated amide groups of H2pydione were both isolated. In the former case the metal ion has a distorted octahedral coordination sphere; in the latter case the complex adopts a pentagonal-bipyramidal geometry. NMR experiments show that the protonation state of the ligand is preserved in a dimethyl sulfoxide (DMSO) solution. The complexes maintain a high-spin state even at low temperatures. Detailed kinetic studies of oxygenation of the iron(II) complexes showed that the deprotonation state of the complex has a profound effect on the reactivity with dioxygen. Oxygenation of the dideprotonated complex of iron(II), Fe(pydioneN5), in aprotic solvents proceeds via a path that is analogous to that of iron(II) porphyrins: via iron(III) superoxo and diiron(III) peroxo species, as evidenced by the spectral changes during the reaction, which is second-order in the concentration of the iron(II) complex, and with an inverse dependence of the reaction rate on the concentration of dioxygen. The final products of oxygenation are crystallographically characterized iron(III) mu-oxo dimers. We have also found that the presence of 1-methylimidazole stabilizes the diiron peroxo intermediate. The reaction of Fe(pydioneN5) with dioxygen in methanol is distinctly different under the same conditions. The reaction is first-order in both iron(II) complex and dioxygen, and no intermediate is spectroscopically observed. Similar behavior was observed for the monodeprotonated complex Fe(HpydioneN5)(Cl). The presence of an accessible proton either from the solvent (reactions in methanol) or from the complex itself (in Fe(HpydioneN5)(Cl)) proves sufficient to alter the oxygenation pathway in these macrocyclic systems, which is reminiscent of the properties of iron(II) porphyrin complexes. The new amidopyridine macrocycles can be considered as new members of the "expanded porphyrin analogue" family. The expansion of the cavity provides control over the spin state and availability of protons. These macrocyclic systems also allow for easy synthetic modifications, paving the way to new, versatile metal complexes.     

NMR investigation of complex formation between metalloporphyrins and π-donors

The formation of molecular complexes between Co(II), Fe(III), and Mn(III) porphyrins and -donors in chloroform solution has been investigated using¹H NMR. It was shown that their stability is controlled to a large extent by the dimensions of the -donor; interaction of the porphyrins with phenanthroline and anthracene, which contain a condensed aromatic system, is substantially more effective than interaction with benzene-derivative -donors. In the case of Co(II) and Fe(III) porphyrins the affinity to it-acceptors is much more pronounced than the affinity to -donors, whereas the acetate of Mn(III) hematoporphyrin forms molecular complexes with phenanthroline, anthracene, and trinitrobenzene with similar stability constants.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 8, pp. 1755–1760, August, 1990.     

Potentiometric, spectroscopic and thermal studies on the metal chelates of 1-(2-thiazolylazo)-2-naphthalenol

The synthesis and characterization of Mn(II), Fe(III), Co(II), Ni(II), Cu(II), Zn(II), Cd(II), Pd(II) and UO2(II) chelates of 1-(2-thiazolylazo)-2-naphthalenol (TAN) were reported. The dissociation constants of the ligand and the stability constants of the metal complexes were calculated pH-metrically at 25 degrees C and 0.1 M ionic strength. The solid complexes were characterized by elemental and thermal analyses, molar conductance, IR, magnetic and diffuse reflectance spectra. The complexes were found to have the formulae [M(L)2] for M = Mn(II), Co(II), Ni(II), Zn(II) and Cd(II); [M(L)X].nH2O for M = Cu(II) (X = AcO, n = 3), Pd(II) (X = Cl, n = 0) and UO2(II) (X = NO3, n = 0), and [Fe(L)Cl2(H2O)].2H2O. The molar conductance data reveal that the chelates are non-electrolytes. IR spectra show that the ligand is coordinated to the metal ions in a terdentate manner with ONN donor sites of the naphthyl OH, azo N and thiazole N. An octahedral structure is proposed for Mn(II), Fe(III), Co(II), Ni(II), Zn(II), Cd(II) and UO2(II) complexes and a square planar structure for Cu(II) and Pd(II) complexes. The thermal behaviour of these chelates shows that water molecules (coordinated and hydrated) and anions are removed in two successive steps followed immediately by decomposition of the ligand molecule in the subsequent steps. The relative thermal stability of the chelates is evaluated. The final decomposition products are found to be the corresponding metal oxides. The thermodynamic activation parameters, such as E*, delta H*, delta S* and delta G* are calculated from the TG curves.     

Complexes of cytotoxic chelators from the dipyridyl ketone isonicotinoyl hydrazone (HPKIH) analogues

In an effort to better understand the antiproliferative effects of the tridentate hydrazone chelators di-2-pyridyl ketone isonicotinoyl hydrazone (HPKIH) and di-2-pyridyl ketone benzoyl hydrazone (HPKBH), we report the coordination chemistry of these ligands with the divalent metal ions, Mn, Co, Ni, Cu, and Zn. These complexes are compared with their Fe(II) analogues which were reported previously. The crystal structures of Co(PKIH)(2), Ni(PKIH)(2), Cu(PKIH)(2), Mn(PKBH)(2), Ni(PKBH)(2), Cu(PKBH)(2), and Zn(PKBH)(2) are reported where similar bis-tridenate coordination modes of the ligands are defined. In pure DMF, all complexes except the Zn(II) compounds exhibit metal-centered M(III/II) (Mn, Fe, Co, Ni) or M(II/I) (Cu) redox processes. All complexes show ligand-centered reductions at low potential. Electrochemistry in a mixed water/DMF solvent only elicited metal-centered responses from the Co and Fe complexes. Remarkably, all complexes show antiproliferative activity against the SK-N-MC neuroepithelioma cell line similar to (HPKIH) or significantly greater than that of the (HPKBH) ligand which suggests a mechanism that does not only involve the redox activity of these complexes. In fact, we suggest that the complexes act as lipophilic transport shuttles that allow entrance to the cell and enable the delivery of both the ligand and metal which act in concert to inhibit proliferation.