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Although directly relevant to metal mediated biological nitrification as well as the coordination chemistry of peroxide, the metal complexes of hydroxylamines and their functionalized variants remain largely unexplored. The chelating hydroxylamine ligand N,N-bis(2-{pyrid-2-ylethyl})hydroxylamine can be readily generated via a solvent free reaction in high purity; however, the ligand is prone to decomposition which can hamper metal reaction. N,N-bis(2-{pyrid-2-ylethyl})hydroxylamine forms stable complexes with chromium(III), manganese(II), nickel(II), and cadmium(II) ions, coordinating in a side-on mode in the case of chromium and via the nitrogen in the case of the latter three metal ions. The hydroxylamine ligand can also be reduced to form N,N-bis(2-{pyrid-2-ylethyl})amine upon exposure to a stoichiometric amount of the metal salts cobalt(II) nitrate, vanadium(III) chloride, and iron(II) chloride. In the reaction with cobalt nitrate, the reduced ligand then chelates to the metal to form [N,N-bis(2-{pyrid-2-ylethyl})amine]dinitrocobalt(II). Upon reaction with vanadium(III) chloride and iron(III) chloride, the reduced ligand is isolated as the protonated free base, resulting from a metal-mediated decomposition reaction.

The reaction of Re(CO)(5)Br with tris(2-pyridyl)methanol (tpmOH) leads to unexpectedly complex chemistry with three new compounds forming instead of a single product. In compound 1, the tpmOH ligand binds to the metal in the N,N',N''-mode; 2 has tpmO(-) bound in the N,N',O-mode; while 3 is a dimer with the tpmO(-) ligand utilizing each of the four donor atoms to bridge the two metal centers. The analogous methyl ether ligands, tris(2-pyridyl)methoxymethane (tpmOMe) or tris[2-(l-methylimidazolyl)]methoxymethane (timmOMe), each yielded a single product, 4 and 5, respectively, bound in the N,N',N''-mode, and are new leads for potential radiotherapeutic agents. All compounds have been structurally characterized.

The reactions of ammonia, pyridine (py), N-methyl imidazole (N-MeIm), tetrahydrothiophene (tht), and piperidine (pip) with Re(CO) 3(H 2O) 3 (+), 1 ( + ), were investigated employing aqueous conditions under atmospheric dioxygen. The reaction of [ 1]Br in aqueous ammonia led to [Re(CO) 3(NH 3) 3]Br ([ 2]Br) as the only product isolated. For the aqueous reactions of [ 1]Br with py, N-MeIm, and tht, mixtures of products are formed because of competition between the bromide and added ligand, even when the ligand is present in excess. Substitution of the PF 6 (-) anion for Br (-) leads to the clean formation of [Re(CO) 3L 3][PF 6] ([ 3][PF 6]-[ 5][PF 6]) for py, N-MeIm, and tht, respectively, as the only products observed. Reaction of [ 1][PF 6] with pip produces the dimeric species, (pip)(CO) 3Re(micro-OH) 2Re(CO) 3(pip), 6. Reactions of [ 1]Br were also performed in methanol for comparison purposes. The reaction with pip in this solvent led to the analogous dimer, (pip)(CO) 3Re(micro-OMe) 2Re(CO) 3(pip), 7; however, reactions with py, N-MeIm, and tht gave Re(CO) 3L 2Br, 8- 10, respectively, as the only products. The crystal structures of compounds [ 2]Br- 10 are reported.

Three different aniline derivatives, namely m- and p-aminobenzoic acids and m-amino benzenesulfonic acid, were sequestered in between layers of a borate-based coordination polymer, based on lead(II) tetrakis(imidazolyl)borate. The aniline derivatives pre-organized in the interlayer spacing of the coordination polymer, and the reactivity of these pre-organized anionic monomers in the crystalline state was studied. We found that thermally activated reactivity under ambient atmospheric oxygen promotes what appears to be polymerization, and that the most reactive species is m-aminobenzenesulfonic acid monomer due to its increased mobility within the layers of the polymer.

The syntheses and structural elucidations of three different cobalt complexes of m-benziphthalocyanine are reported; both Co(II) and Co(III) complexes can be generated, and the ring undergoes partial oxidation upon metalation with Co(OAc)2x4H2O.

Three Re(I) complexes (3, 5, and 7) (Re(CO)3Cl(L)2) and three new Pt(II) complexes (4, 6, and 8) ([Pt(P(Et)3)2(L)2](OTf)2), where L = pyridine, 1 (4-Py-EDOT) or 2 (4-Py-bithiophene), were prepared and characterized. The solid-state structures of 4 and 5 were determined by X-ray crystallography. Electrochromic polymeric films of 2, 5, and 6 were prepared and characterized.

The metallation of the core-modified phthalocyanine analogue dicarbahemiporphyrazine with manganese, iron, and cobalt results in the formation of low-coordinate metal(II) complexes. All three compounds are produced by the reaction of metal carbonyls with the free base macrocycle. As in many other carbaporphyrinoids, the internal C-H bonds remain intact upon metallation, resulting in the formation of two long-range agostic-type interactions. Each metal can thus be considered as a three-coordinate ion, where two inner isoindolene nitrogens and a single axial pyridine are bound to the metal. The manganese and cobalt complexes, Mn(dchp)py and Co(dchp)py, are nearly isostructural, but the iron complex, Fe(dchpH2)py, exhibits a reduction at an iminic double bond upon metallation.

The formation of vanadium(III) complexes with nuclearity greater than two is believed to occur in aqueous solution on the basis of potentiometric, electrochemical, and/or UV-vis spectroscopy titration measurements, although structural evidence for this is limited. Upon the addition of 1-2 equiv of acetate, propionate, chloroacetate, trifluoroacetate, or bromoacetate to an aqueous, acidic solution of vanadium(III), trinuclear and tetranuclear complexes are formed. The structures of [V4(mu-OH)4(mu-OOCCF3)4(OH2)8]Cl4.7.5H2O (1), [V4(mu-OH)4(mu-OOCCH3)4(OH2)8]Cl4.CH3COOH.12H2O (2), [V4(mu-OH)4(mu-OOCCH3)4(OH2)8]Cl4.3H2O (3), [V3(mu3-O)(mu-OOCCH2Br)6(OH2)3]CF3SO3.H2O (4), [V3(mu3-O)(mu-OOCCH2CH3)6(OH2)3]Cl.2H2O (5), [V3(mu3-O)(mu-OOCCH3)6(OH2)3]Cl.3.5H2O (6), and [V3(mu3-O)(mu-OOCCH2Cl)6(OH2)3]CF3SO3.H2O (7) have been determined by X-ray diffraction. Importantly, electrospray mass spectrometry and 1H NMR measurements suggest that these complexes are not purely solid-state phenomena but are also present in solution. For the vanadium(III)/acetate and vanadium(III)/propionate systems, two paramagnetic 1H NMR signals corresponding to two distinct complexes (species A and B) are observed in the 40-55 ppm region for 0.20 mol equiv of acetate or propionate, at pD 3.44. No corresponding signals are observed for the vanadium(III)/bromoacetate and vanadium(III)/chloroacetate systems under the same conditions or for the vanadium(III)/ trifluoroacetate system using 19F NMR spectroscopy. UV-vis spectra suggest that species B are structurally analogous for the vanadium(III)/acetate and vanadium(III)/propionate systems, whereas structurally different complexes are the major species for the other systems. Diffusion coefficients of species B for the vanadium(III)/acetate and vanadium(III)/propionate systems determined by pulsed-field-gradient spin-echo NMR spectroscopy measurements are (3.0 +/- 0.1) x 10-6 and (3.23 +/- 0.01) x 10-6 cm2 s-1, respectively, and are most consistent with species B being trimeric, rather than tetranuclear, complexes.

Re(CO)3L compounds, where L is a methane-derivatized tripodal ligand, can be prepared under aqueous conditions, and one of which displays significant stability under physiological conditions.

The photophysical characterization of the two tautomers (1e and 1i) of 5,10,15,20-tetraphenyl N-confused free-base porphyrin, as well as the tautomer-locked 2-methyl 5,10,15,20-tetraphenyl N-confused free-base porphyrin, was carried out using a combination of steady state and time-resolved optical techniques. N-Confused porphyrins, alternatively called 2-aza-21-carba-porphyrins or inverted porphyrins, are of great interest for their potential as building blocks in assemblies designed for artificial photosynthesis, and understanding their excited-state properties is paramount to future studies in multicomponent arrays. Femtosecond resolved transient absorption experiments reveal spectra that are similar to those of tetraphenylporphyrin (H2TPP) with either Soret or Q-band excitation, with an extinction coefficient for the major absorbing band of 1e that was about a factor of 5 larger than that of H2TPP. The lifetime of the S1 state was determined at a variety of absorption wavelengths for each compound and was found to be consistent with time-resolved fluorescence experiments. These experiments reveal that the externally protonated tautomer (1e) is longer lived (tau = 1.84 ns) than the internally protonated form (1i, tau = 1.47 ns) by approximately 369 ps and that the N-methyl N-confused porphyrin was shorter lived than the tautomeric forms by approximately 317 ps (DMAc) and approximately 396 ps (benzene). Steady-state fluorescence experiments on tautomers 1e and 1i and the N-methyl analogues corroborate these results, with fluorescence quantum yields (Phi(Fl)) of 0.046 (1e, DMAc) and 0.023 (1i, benzene), and 0.025 (DMAc) and 0.018 (benzene) for the N-methyl N-confused porphyrin. The lifetime and quantum yield data was interpreted in terms of structural changes that influence the rate of internal conversion. The absorption and transient absorption spectra of these porphyrins were also examined in the context of DFT calculations at the B3LYP/6-31G(d)//B3LYP/3-21G(d) level of theory and compared to the spectra/electronic structure of H2TPP and tetraphenyl chlorin.

Recently, metal complexes of the isomers and analogs of porphyrin have become important model compounds for heme enzymes and proteins. While the chemistry of metalloporphyrins as heme models still attracts attention, the isomers and analogs of porphyrins provide insight into the biological choice of porphine as the macrocycle of choice and also help model reactive intermediates, such as high valent oxidation states. In this mini-review, we discuss the heme-relevant chemistry of N-confused porphyrin, an isomer of porphyrin with an inverted pyrrole ring, and focus on the chemistry of manganese, iron, and cobalt. The metallation chemistry of this macrocycle is more diverse than normal porphyrin, and involves tautomerization, C-H bond activation, the Lewis basicity of the external nitrogen, and issues with nucleophilic sensitivity. Despite the challenges posed by N-confused porphyrin, significant progress has been made toward generating heme-model complexes with this macrocycle.

Three divalent closed d shell metal complexes of the hydrotris(methimazolyl)borate ligand, [Ca(mt)2].6H2O, [Ba(mt)2](H2O)2, and Hg4(mt)4Cl4, were synthesized and characterized by single crystal X-ray diffraction; the three structures reveal very different ligand binding modes for each metal ion.

[reaction: see text] An improved methodology for the N-alkylation of the porphyrin isomer N-confused porphyrin is presented. The combination of polar solvent conditions and the use of the base Cs2CO3 affords externally modified products in high yield without separation difficulties and without the use of large excesses of alkylating reagent. The further transformation and metalation of these products provides opportunities for the construction of metalloenzyme model complexes, peptide adducts, and chromophore assemblies.

We have synthesized the first early transition metal N-confused porphyrin complex Mo(NCTPP)(pip)2; this species is isostructural to its normal porphyrin analog Mo(TPP)(pip)2 but exhibits significant electronic differences arising from the inversion of a single pyrrolic group.

Metal-organic frameworks based on the Pb[B(Im)(4)](+) unit form layered structures analogous to those observed in clays and double layered hydroxide minerals. These layers can act as scaffolds for the organization of anionic organic guests. In this report, we use this scaffold to assemble TEMPO and PROXYL carboxylates in the interlayer spacings of Pb[B(Im)(4)](4-carboxy-TEMPO) 1 and Pb[B(Im)(4)](3-carboxy-PROXYL)(H(2)O)2, respectively. The resultant materials are paramagnetic, and the organization of the radical units differs between the two compounds. This results in changes in electronic structure of the radical unit, as observed by EPR spectroscopy.

Four free-base corroles with electron-donating or electron-withdrawing groups on the para or 2 through 6-positons of the meso phenyl rings were prepared via either Paolesse or Gross conditions and investigated for their absorption and emission properties. The triaryl corroles 5,10,15-triphenylcorrole, 5,10,15-tris(pentafluorophenyl)corrole, 5,10,15-tris(p-nitrophenyl)corrole, and 5,10,15-tris(p-methoxyphenyl)corrole were examined. Absorption, steady-state, and time-resolved fluorescence measurements were performed on all compounds in both nonpolar (dichloromethane) and polar (dimethylacetamide) solvents. The experimental evidence points to hydrogen bonding with an internal N-H group as the most likely factor in the solvent-dependent photophysical behavior of these corroles, that is also highly dependent upon substitution.

We report the first structures of simple acetate complexes of vanadium(III) formed in aqueous solution. Paramagnetic (1)H NMR spectroscopy titration experiments indicate the formation of two major V(III)/acetate complexes in acidic aqueous solution for acetate/V(III) < or =4, pD 3.50. A novel tetranuclear cluster and a trinuclear cluster have been characterized by X-ray diffraction studies. Mass spectrometry measurements show these clusters retain their integrity in solution.

A series of oxalato-bridged dinuclear copper(II) complexes of the general formula [Cu2(Pz2CPh2)2(X)2(mu-C2O4)] (X = Cl- (1), NO3(-) (2), ClO4(-) (3); Pz2CPh2 = diphenyldipyrazolylmethane) or [Cu2(Pz(3m)2CPh2)2(H2O)2(mu-C2O4)](NO3)2 x H2O (4) (Pz(3m)2CPh2 = diphenylbis(3-methylpyrazolyl)methane) was synthesized where the axial ligand was systematically varied to study its effect on structure and magnetic coupling. The structures of compounds 1, 2, and 4 have been elucidated by single-crystal X-ray diffraction. [Cu2(Pz2CPh2)2(Cl)2(mu-C2O4)] and [Cu2(Pz2CPh2)2(NO3)2(mu-C2O4)] are isostructural and crystallize in the triclinic system, space group P, Z = 2, with a = 8.6155(8) A, b = 10.1435(9) A, c = 11.3612(11) A, alpha = 95.535(2) degrees, beta = 110.303(2) degrees, and gamma = 106.111(2) degrees for 1 and with a = 8.863(7) A, b = 10.241(9) A, c = 11.425(10) A, alpha = 98.985(14) degrees, beta = 110.449(13) degrees, and gamma = 103.664(14) degrees for 2. [Cu2(Pz(3m)2CPh2)2(H2O)2(mu-C2O4)] x NO3 x H2O crystallizes in the monoclinic system, space group C2/c, Z = 4, with a = 23.4588(14) A, b = 8.8568(5) A, c = 21.7818(13) A, alpha = gamma = 90 degrees, and beta = 100.8890(10) degrees. Variable-temperature magnetic susceptibility studies indicate that all four compounds are strongly antiferromagnetically coupled (2J/k = -364, -344 cm(-1) (2), -424 cm(-1) (3), and -378 cm(-1) (4)). Magnetic and EPR results are discussed with respect to structural parameters to explore possible magneto-structural correlations.

Crystals of the layered metal organic framework solid Pb[B(Im)4](NO3)(nH2O) can undergo exchange of the nitrate for perrhenate, a model for pertechnetate, forming Pb[B(Im)4](ReO4). We can monitor this reaction by 207Pb solid-state NMR and can isolate single crystals of the resultant material through growth in the presence of an excess of perrhenate. Such a synthetic metal-organic framework solid represents a new candidate for pertechnetate-sequestering materials.

We report the first high-frequency and -field electron paramagnetic resonance (HFEPR) study of a Mn(III) N-confused porphyrin (NCP) complex (NCP is also known as inverted porphyrin or 2-aza-21-carbaporphyrin). We have found a striking variation in the electronic properties of the S = 2 Mn(III) ion coordinated by NCP compared to other Mn(III) porphyrinoid complexes. Thus, inversion of a single pyrrole ring greatly changes the equatorial ligand field exerted and leads to large magnitudes of both the axial and rhombic zero-field splitting [respectively, D = -3.084(3) cm(-1), E = -0.608(3) cm(-1)], which are unprecedented in other Mn(III) porphyrinoids.

A manganese(III) complex of tetraphenylporpholactone, Mn(TPPL)Cl, was synthesized and characterized, including by single-crystal X-ray diffraction; the catalytic activity of this complex for olefin epoxidation reactions is compared with that of manganese(III) tetraphenylporphyrin chloride, Mn(TPP)Cl.

A series of N-confused tetraphenylporphyrins (H(2)NCTPPs) with substituents on either the para- or the 3,5-positions of the meso phenyl rings were prepared using Lindsey conditions. Both electron-withdrawing and electron-donating groups were chosen in order to probe the effects of peripheral substitution on the properties of the macrocycles. The series includes 5,10,15,20-tetra-(4-R-phenyl) N-confused porphyrins (where R = bromo (1), iodo (2), cyano (3), methoxy (4), 2',5'-dimethoxyphenyl (5), or ethynyl (6)) and 5,10,15,20-(3,5-di-tert-butylphenyl) N-confused porphyrin (7). Absorption and steady-state fluorescence measurements were carried out, and quantum yields were measured for all compounds in both dichloromethane (CH(2)Cl(2)) and dimethylacetamide (DMAc).

We report the syntheses of cobalt N-confused porphyrins; this work completes the series of the late first-row transition metals that have been incorporated into the core of N-confused porphyrin, and in these compounds the macrocycles can act as either a -2 or -3 anion.

We are using the coordinating anions tetrakis(imidazolyl)borate and tetrakis(4-methylimidazolyl)borate to construct new metal-organic framework structures. In this report, we are exploring materials similar in composition to the previously reported layered network structure Pb[B(Im)(4)](NO(3))(nH(2)O). The metal in this compound can be replaced with isoelectronic Tl(I), affording Tl[B(Im)(4)], and the borate can be modified by using 4-methylimidazole, resulting in Pb[B(4-MeIm)(4)](NO(3)) and Tl[B(4-MeIm)(4)]. Like the parent Pb[B(Im)(4)](NO(3))(nH(2)O), Tl[B(Im)(4)] and Tl[B(4-MeIm)(4)] are layered network structures but both lack anions or solvent molecules in the interlayer spacing. The material Pb[B(4-MeIm)(4)](NO(3)), however, exhibits a 3D network structure that lacks an open topology, resulting from the increased stereochemical activity (greater steric bulk toward other ligands) of the 4-methylimidazole ring. Both of the Tl(I) solids display longer M-N bonds than observed in the analogous Pb(II) compounds; these lengths account for the decreased effect of the stereochemical activity of the 4-methylimidazole ring in Tl[B(4-MeIm)(4)].

The coordination polymer Pb[B(Im)(4)](NO(3))(xH(2)O), constructed by using sodium tetrakis(imidazolyl)borate and lead(II) nitrate solutions, is a layered material with the metal centers facing the interlayer spacing. As in naturally occurring layered minerals, this compound can readily undergo anion exchange and reversible intercalation of solvent water in the solid state with retention of crystallinity. We observed changes in solvent intercalation by (207)Pb solid state NMR (SSNMR) and thermogravimetric analysis (TGA). Stoichiometric exchange of (15)N nitrate for nitrate and iodide for nitrate is monitored by (15)N and (207)Pb SSNMR, and single crystals of the iodide-exchanged material Pb[B(Im)(4)]I were isolated. While the iodide compound can be obtained through facile exchange from the nitrate parent compound, the organic anion benzoate is placed in the interlayer spacing for nitrate under self-assembly conditions and forms an alternating monolayer in Pb[B(Im)(4)](C(6)H(5)COO)(0.5H(2)O). The ion exchange versus self-assembly behavior correlates with the structural differences in the three compounds. In both Pb[B(Im)(4)]I and Pb[B(Im)(4)](C(6)H(5)COO)(0.5H(2)O), the lead sites act as Lewis acids for the iodide and benzoate, respectively.

Manganese N-confused porphyrins activate C-C and C-H bonds upon heating or air oxidation; the dimer complex [Mn(NCTPP)]2 is reduced at two meso positions, and the pyridine coordinated monomer breaks the internal C-H bond upon heating or exposure to oxygen.

We are using the coordinating anion tetrakis(imidazolyl)borate to construct new metal-organic framework structures. In this report, we present three alkaline earth metal network solids incorporating this anion. All three compounds have the same formula, M[B(Im)(4)](2)(H(2)O)(2) (M = Mg, Ca, Sr), and the same coordination environment about the metal. However, the three compounds have different network structures with different degrees of hydrogen bonding; the Mg material forms a two-dimensional network and the Ca and Sr compounds form one-dimensional chains. In addition, we present the structure of the protonated anion B(HIm)(Im)(3) as a model for the default structure of this anion and discuss how the conformation of tetrakis(imidazolyl)borate can affect the structure of network solids.

The coordination polymer Pb[B(Im)(4)](NO(3)), constructed by using tetrakis(imidazolyl)borate and lead(II) nitrate solutions, is a layered material with the metal centers facing the interlayer spacing. As in naturally occurring layered minerals, this compound can readily undergo anion exchange in the solid state with retention of crystallinity. We examined stoichiometric exchange of (15)N-nitrate for nitrate and iodide for nitrate by (15)N and (207)Pb SSNMR and confirmed retention of crystallinity by IR and powder XRD diffraction.

The synthesis and structural characterization of a manganese adduct of N-confused tetraphenylporphyrin (NCTPP) is presented; in the absence of coordinating ligands this complex forms a novel dimer structure and demonstrates a potential manganese agostic interaction with the interior pyrrolic CH as seen in other first row transition metal NCTPP compounds.

The anion BF(CN)3-forms isomorphous network polymers with Cu(I) and Ag(I) that exhibit one-dimensional channels along the b axis and demonstrate stability to air and light respectively.

Platinum drugs play an important role in the treatment of cancer, but there is room for improvement. Here we present a new platinum drug-discovery strategy to identify compounds having efficacy equivalent to that of cisplatin with the expectation that some may increase the spectrum of treatable tumors and/or reduce dose-limiting toxicity. Platinum drug candidates were generated through the use of automated synthesis, taking advantage either of the trans effect or by using silver chloride precipitation to activate the starting materials. Reaction products were screened for activity in a high-throughput transcription assay and the most promising candidates characterized. Over 3,600 reaction products were screened for their ability to inhibit transcription of beta-lactamase in the BlaM HeLa cell line by monitoring cleavage of a lactam ring linking the two halves of a fluorescent resonance energy transfer (FRET) dye, CCF2/AM. From this screen, three reactions produced good candidates, and four species were identified among these reaction products. Three of the compounds, cis-[(isopropylamine)2PtCl2], cis-[(cyclobutylamine)2PtCl2], and cis-[ammine(cyclobutylamine)PtCl2], have been previously determined to be active cisplatin analogs. The fourth compound, cis-[ammine(2-amino-3-picoline)PtCl2], represents a new kind of antitumor drug candidate similar to ZD0473, a recently reported analog. The discovery of these compounds represents an important proof of principle that platinum anticancer drug candidates can be rapidly prepared and screened in this manner.

The compound [Pt(lysine)Cl2] (Kplatin) was previously identified in a study of platinum amino acid complexes as a potential antitumor drug candidate. The DNA binding properties, high mobility group (HMG)-domain protein affinity for the platinated DNA, and cytotoxicity against HeLa cells of Kplatin and three related (N,O) chelated platinum(II) amino acid complexes, [Pt(arginine)Cl2] (Rplatin), K[Pt(Nepsilon-acetyllysine)Cl2] (NacKplatin), and K[Pt(norleucine)Cl2] (Norplatin), are reported. The four complexes have identical PtCl2(N,O) coordination environments. A new solid phase screening methodology was devised in which platinated DNA probes are covalently attached to a nylon support and tested for their ability to bind a fluorescently labeled HMG-domain protein. The fluorescent HMG-domain protein was generated by expressing a fusion of the green fluorescent protein (GFP) with recombinant rat HMG1. Binding revealed by the solid phase method correlated well with the results of gel mobility shift and HeLa cytotoxicity assays. These results suggest that the net charge on the complex, rather than the nature of the side chain, is the most important factor underlying the DNA binding properties and toxicity of amino acid (N,O) chelated platinum complexes. This property explains why Kplatin was previously selected from the pool of platinum amino acid complexes based on the ability of its DNA adducts to bind HMG1.