Reactions of dicobalt octacarbonyl with dinucleating and mononucleating bis(imino)pyridine ligands.

This work focuses on the application of dicobalt octacarbonyl (Co2(CO)8) as a metal precursor in the chemistry of formally low-valent cobalt with redox-active bis(imino)pyridine [NNN] ligands. The reactions of both mononucleating mesityl-substituted bis(aldimino)pyridine (L1) and dinucleating macrocyclic xanthene-bridged di(bis(aldimino)pyridine) (L2) with Co2(CO)8 were investigated. Independent of the metal-to-ligand ratio (1 : 1 or 1 : 2 ligand to Co2(CO)8), the reaction of the dinucleating ligand L2 with Co2(CO)8 produces a tetranuclear complex [Co4(L2)(CO)10] featuring two discrete [Co2[NNN](CO)5] units. In contrast, a related mononucleating bis(aldimino)pyridine ligand, L1, produces different species at different ligand to Co2(CO)8 ratios, including dinuclear [Co2(CO)5(L1)] and zwitterionic [Co(L1)2][Co(CO)4]. Interestingly, [Co4(L2)(CO)10] features metal-metal bonds, and no bridging carbonyls, whereas [Co2(CO)5(L1)] contains cobalt centers bridged by one or two carbonyl ligands. In either case, treatment with excess acetonitrile leads to disproportionation to the zwitterionic [Co[NNN](NCMe)2][Co(CO)4] units. The electronic structures of the complexes described above were studied with density functional theory. All the obtained bis(imino)pyridine complexes serve as catalysts for cyclotrimerization of methyl propiolate, albeit their reactivity is inferior compared with Co2(CO)8.

Aluminum dihydride complexes and their unexpected application in atomic layer deposition of titanium carbonitride films.

Aluminum dihydride complexes containing amido-amine ligands were synthesized and evaluated as potential reducing precursors for thermal atomic layer deposition (ALD). Highly volatile monomeric complexes AlH2(tBuNCH2CH2NMe2) and AlH2(tBuNCH2CH2NC4H8) are more thermally stable than common Al hydride thin film precursors such as AlH3(NMe3). ALD film growth experiments using TiCl4 and AlH2(tBuNCH2CH2NMe2) produced titanium carbonitride films with a high growth rate of 1.6-2.0 Å per cycle and resistivities around 600 µΩ cm within a very wide ALD window of 220-400 °C. Importantly, film growth proceeded via self-limited surface reactions, which is the hallmark of an ALD process. Root mean square surface roughness was only 1.3% of the film thickness at 300 °C by atomic force microscopy. The films were polycrystalline with low intensity, broad reflections corresponding to the cubic TiN/TiC phase according to grazing incidence X-ray diffraction. Film composition by X-ray photoelectron spectroscopy was approximately TiC0.8N0.5 at 300 °C with small amounts of Al (6 at%), Cl (4 at%) and O (4 at%) impurities. Remarkably, self-limited growth and low Al content was observed in films deposited well above the solid-state thermal decomposition point of AlH2(tBuNCH2CH2NMe2), which is ca. 185 °C. Similar growth rates, resistivities, and film compositions were observed in ALD film growth trials using AlH2(tBuNCH2CH2NC4H8).

Photophysical characterization of a highly luminescent divalent-europium-containing azacryptate.

We report a new luminescent EuII-containing complex. The complex is excited with visible light, leading to emission centered at 447 nm with a lifetime of 1.25 µs. Computational studies suggest that the steric bulk of the ligand is a major factor influencing the wavelength of emission.

Unusual Role of Excited State Mixing in the Enhancement of Photoinduced Ligand Exchange in Ru(II) Complexes.

Four Ru(II) complexes were prepared bearing two new tetradentate ligands, cyTPA and 1-isocyTPQA, which feature a piperidine ring that provides a structurally rigid backbone and facilitates the installation of other donors as the fourth chelating arm, while avoiding the formation of stereoisomers. The photophysical properties and photochemistry of [Ru(cyTPA)(CH3CN)2]2+ (1), [Ru(1-isocyTPQA)(CH3CN)2]2+ (2), [Ru(cyTPA)(py)2]2+ (3), and [Ru(1-isocyTPQA)(py)2]2+ (4) were compared. The quantum yield for the CH3CN/H2O ligand exchange of 2 was measured to be Φ400 = 0.033(3), 5-fold greater than that of 1, Φ400 = 0.0066(3). The quantum yields for the py/H2O ligand exchange of 3 and 4 were lower, 0.0012(1) and 0.0013(1), respectively. DFT and related calculations show the presence of a highly mixed 3MLCT/3ππ* excited state as the lowest triplet state in 2, whereas the lowest energy triplet states in 1, 3, and 4 were calculated to be 3LF in nature. The mixed 3MLCT/3ππ* excited state places significant spin density on the quinoline moiety of the 1-isocyTPQA ligand positioned trans to the photolabile CH3CN ligand in 2, suggesting the presence of a trans-type influence in the excited state that enhances ligand exchange. Ultrafast spectroscopy was used to probe the excited states of 1-4, which confirmed that the mixed 3MLCT/3ππ* excited state in 2 promotes ligand dissociation, representing a new manner to effect photoinduced ligand exchange. The findings from this work can be used to design improved complexes for applications that require efficient ligand dissociation, as well as for those that require minimal deactivation of the 3MLCT state through low-lying metal-centered states.

Structural Features of Europium(II)-Containing Cryptates That Influence Relaxivity.

EuII -containing complexes were studied with respect to properties relevant to their use as contrast agents for magnetic resonance imaging. The influences of molecular parameters and field strength on relaxivity were studied for a series of EuII -containing cryptates and their adducts with ß-cyclodextrins, poly-ß-cyclodextrins, and human serum albumin. Solid- and solution-phase characterization of EuII -containing complexes is presented that demonstrates the presence of inner-sphere molecules of water. Additionally, relaxivity, water-exchange rate, rotational correlation time, and electronic relaxation times were determined using variable-temperature 17 O NMR, nuclear magnetic relaxation dispersion, and electron paramagnetic resonance spectroscopic techniques. These results are expected to be instrumental in the design of future EuII -based contrast agents.

Synthesis of bimetallic trifluoroacetates through a crystallochemical investigation of their monometallic counterparts: the case of (A, A')(CF3COO)2·nH2O (A, A' = Mg, Ca, Sr, Ba, Mn).

Owing to their potential as single-source precursors for compositionally complex materials, there is growing interest in the rational design of multimetallic compounds containing fluorinated ligands. In this work, we show that chemical and structural principles for a materials-by-design approach to bimetallic trifluoroacetates can be established through a systematic investigation of the crystal-chemistry of their monometallic counterparts. A(CF3COO)2·nH2O (A = Mg, Ca, Sr, Ba, Mn) monometallic trifluoroacetates were employed to demonstrate the feasibility of this approach. The crystal-chemistry of monometallic trifluoroacetates was mapped using variable-temperature single-crystal X-ray diffraction, powder X-ray diffraction, and thermal analysis. The evolution with temperature of the previously unknown crystal structure of Mg(CF3COO)2·4H2O was found to be identical to that of Mn(CF3COO)2·4H2O. More important, the flexibility of Mnx(CF3COO)2x·4H2O (x = 1, 3) to adopt two structures, one isostructural to Mg(CF3COO)2·4H2O, the other isostructural to Ca3(CF3COO)6·4H2O, enabled the synthesis of Mg-Mn and Ca-Mn bimetallic trifluoroacetates. Mg0.45Mn0.55(CF3COO)2·4H2O was found to be isostructural to Mg(CF3COO)2·4H2O and exhibited isolated metal-oxygen octahedra with Mg2+ and Mn2+ nearly equally distributed over the metal sites (Mg/Mn: 45/55). Ca1.72Mn1.28(CF3COO)6·4H2O was isostructural to Ca3(CF3COO)6·4H2O and displayed trimers of metal-oxygen corner-sharing octahedra; Ca2+ and Mn2+ were unequally distributed over the central (Ca/Mn: 96/4) and terminal (Ca/Mn: 38/62) octahedral sites.

Effects of Methyl Substitution in Ruthenium Tris(2-pyridylmethyl)amine Photocaging Groups for Nitriles.

Four complexes of the general formula [Ru(L)(CH3CN)2](PF6)2, [L = TPA (5), MeTPA (6), Me2TPA (7), and Me3TPA (8)] [TPA = tris[(pyridin-2-yl)methyl]amine, where methyl groups were introduced consecutively onto the 6-position of py donors of TPA, were prepared and characterized by various spectroscopic techniques and mass spectrometry. While 5 and 8 were isolated as single stereoisomers, 6 and 7 were isolated as mixtures of stereoisomers in 2:1 and 1.5:1 ratios, respectively. Steric effects on ground state stability and thermal and photochemical reactivities were studied for all four complexes using (1)H NMR and electronic absorption spectroscopies and computational studies. These studies confirmed that the addition of steric bulk accelerates photochemical and thermal nitrile release.

Synthesis of a mononuclear, non-square-planar chromium(ii) bis(alkoxide) complex and its reactivity toward organic carbonyls and CO2.

In this paper, we report the synthesis and reactivity of a rare mononuclear chromium(ii) bis(alkoxide) complex, Cr(OR')2(THF)2, that is supported by a new bulky alkoxide ligand (OR' = di-t-butyl-(3,5-diphenylphenyl)methoxide). The complex is prepared by protonolysis of square-planar Cr(N(SiMe3)2)2(THF)2 with HOR'. X-ray structure determination disclosed that Cr(OR')2(THF)2 features a distorted seesaw geometry, in contrast to nearly all other tetra-coordinate Cr(ii) complexes, which are square-planar. The reactivity of Cr(OR')2(THF)2 with aldehydes, ketones, and carbon dioxide was investigated. Treatment of Cr(OR')2(THF)2 with two equivalents of aromatic aldehydes ArCHO (ArCHO = benzaldehyde, 4-anisaldehyde, 4-trifluorbenzaldehyde, and 2,4,6-trimethylbenzaldehyde) leads cleanly to the formation of Cr(iv) diolate complexes Cr(OR')2(O2C2H2Ar2) that were characterized by UV-vis and IR spectroscopies and elemental analysis; the representative complex Cr(OR')2(O2C2H2Ph2) was characterized by X-ray crystallography. In contrast, no reductive coupling was observed for ketones: treatment of Cr(OR')2(THF)2 with one or two equivalents of benzophenone forms invariably a single ketone adduct Cr(OR')2(OCPh2) which does not react further. QM/MM calculations suggest the steric demands prevent ketone coupling, and demonstrate that a mononuclear Cr(iii) bis-aldehyde complex with partially reduced aldehydes is sufficient for C-C bond formation. The reaction of Cr(OR')2(THF)2 with CO2 leads to the insertion of CO2 into a Cr-OR' bond, followed by complex rearrangement to form a diamagnetic dinuclear paddlewheel complex Cr2(O2COR')4(THF)2, that was characterized by NMR, UV-vis, and IR spectroscopy, and X-ray crystallography.

Highly Energetic, Low Sensitivity Aromatic Peroxy Acids.

The synthesis, structure, and energetic materials properties of a series of aromatic peroxy acid compounds are described. Benzene-1,3,5-tris(carboperoxoic) acid is a highly sensitive primary energetic material, with impact and friction sensitivities similar to those of triacetone triperoxide. By contrast, benzene-1,4-bis(carboperoxoic) acid, 4-nitrobenzoperoxoic acid, and 3,5-dinitrobenzoperoxoic acid are much less sensitive, with impact and friction sensitivities close to those of the secondary energetic material 2,4,6-trinitrotoluene. Additionally, the calculated detonation velocities of 3,5-dinitrobenzoperoxoic acid and 2,4,6-trinitrobenzoperoxoic acid exceed that of 2,4,6-trinitrotoluene. The solid-state structure of 3,5-dinitrobenzoperoxoic acid contains intermolecular O-H⋅⋅⋅O hydrogen bonds and numerous N⋅⋅⋅O, C⋅⋅⋅O, and O⋅⋅⋅O close contacts. These attractive lattice interactions may account for the less sensitive nature of 3,5-dinitrobenzoperoxoic acid.

Selective Release of Aromatic Heterocycles from Ruthenium Tris(2-pyridylmethyl)amine with Visible Light.

Three complexes of the general formula [Ru(TPA)L2](PF6)2 [TPA = tris(2-pyridylmethyl)amine], where L = pyridine (1), nicotinamide (2), and imidazole (3), were prepared and characterized spectroscopically. X-ray crystallographic data were obtained for 1 and 3. Complexes 1-3 show strong absorption in the visible region and selective release of heterocycles upon irradiation with visible light. Time-dependent density functional theory calculations are consistent with the presence of singlet metal-to-ligand charge-transfer bands in the visible region in 1-3. Caged heterocycles 1-3 are highly stable in solution in the dark, including in cell growth media. Cell viability data show no signs of toxicity of 1-3 against PC-3 cells at concentrations up to 100 µM under light and dark conditions, consistent with Ru(TPA) acting as a nontoxic and effective photocaging group for aromatic heterocycles.

Open-Framework Structures of Anhydrous Sr(CF3COO)2 and Ba(CF3COO)2.

Anhydrous Sr(CF3COO)2 and Ba(CF3COO)2 open-framework structures featuring three-dimensional connectivity of metal-oxygen polyhedra were crystallized from a mixture of water and CF3COOH. Crystallization was induced via evaporation of the solvent mixture under a dry nitrogen flow. This approach differs from that routinely employed for crystallization of metal trifluoroacetates, which achieves solvent evaporation by heating under air and yields hydrated salts. Thermogravimetric and differential thermal analysis as well as single-crystal and synchrotron powder X-ray diffraction were employed to characterize the alkaline-earth trifluoroacetate products. Neither thermal analysis nor single-crystal X-ray diffraction detected the presence of crystallization water molecules, demonstrating these trifluoroacetates can be obtained in anhydrous form. Single-crystal X-ray diffraction studies showed that Sr(CF3COO)2 and Ba(CF3COO)2 are isostructural and crystallize in the rhombohedral R3̅ space group. Both compounds belong to the class of organic-inorganic extended hybrids and exhibit an open-framework structural motif with three-dimensional connectivity of the metal-oxygen polyhedra and one-dimensional channels along the c axis. The channels are decorated with the trifluoromethyl groups of the trifluoroacetate ligands, and their average (minimum) diameters are ∼3.75 (2.60) and 3.45 (2.25) Å for Sr(CF3COO)2 and Ba(CF3COO)2, respectively. This size range is comparable to the kinetic diameter of small molecules such as hydrogen (2.3 Å). Chemical substitution of barium for strontium affects not only the diameter of the channels but also the spatial arrangement of the trifluoromethyl groups within the channels and the coordination environment of the metal atoms. The different coordination requirements of the strontium and barium atoms are accommodated through the displacement of one of the two chemically distinct trifluoroacetate ligands relative to the metal center.

A Eu(II)-Containing Cryptate as a Redox Sensor in Magnetic Resonance Imaging of Living Tissue.

The Eu(II) ion rivals Gd(III) in its ability to enhance contrast in magnetic resonance imaging. However, all reported Eu(II)-based complexes have been studied in vitro largely because the tendency of Eu(II) to oxidize to Eu(III) has been viewed as a major obstacle to in vivo imaging. Herein, we present solid- and solution-phase characterization of a Eu(II)-containing cryptate and the first in vivo use of Eu(II) to provide contrast enhancement. The results indicate that between one and two water molecules are coordinated to the Eu(II) core upon dissolution. We also demonstrate that Eu(II)-based contrast enhancement can be observed for hours in a mouse.

Less sensitive oxygen-rich organic peroxides containing geminal hydroperoxy groups.

A series of oxygen-rich organic peroxide compounds each containing two bis(hydroperoxy)methylene groups is described. Energetic testing shows that these compounds are much less sensitive toward impact and friction than existing classes of organic peroxides. The compounds are highly energetic, which may lead to practical peroxide-based explosives.

Aqueous Eu(II)-Containing Complex with Bright Yellow Luminescence.

Eu(II)-containing materials have unique luminescence, redox, and magnetic properties that have potential applications in optoelectronics, sensors, and imaging. Here, we report the synthesis and characterization of Eu(II)-containing aza-222 cryptate that displays yellow luminescence and a quantum yield of 26% in aqueous media. The crystal structure reveals a staggered hula-hoop geometry. Both solid-state and solution-phase data are presented that indicate that the high quantum yield is a result of the absence of OH oscillators in the inner sphere of the complex. We expect that Eu(II)-containing aza-222 cryptate is a step toward Eu(II)-containing luminescent materials that can be used in a variety of applications including biological imaging.

Reductive elimination of hypersilyl halides from zinc(II) complexes. Implications for electropositive metal thin film growth.

Treatment of Zn(Si(SiMe3)3)2 with ZnX2 (X = Cl, Br, I) in tetrahydrofuran (THF) at 23 °C afforded [Zn(Si(SiMe3)3)X(THF)]2 in 83-99% yield. X-ray crystal structures revealed dimeric structures with Zn2X2 cores. Thermogravimetric analyses of [Zn(Si(SiMe3)3)X(THF)]2 demonstrated a loss of coordinated THF between 50 and 155 °C and then single-step weight losses between 200 and 275 °C. The nonvolatile residue was zinc metal in all cases. Bulk thermolyses of [Zn(Si(SiMe3)3)X(THF)]2 between 210 and 250 °C afforded zinc metal in 97-99% yield, Si(SiMe3)3X in 91-94% yield, and THF in 81-98% yield. Density functional theory calculations confirmed that zinc formation becomes energetically favorable upon THF loss. Similar reactions are likely to be general for M(SiR3)n/MXn pairs and may lead to new metal-film-growth processes for chemical vapor deposition and atomic layer deposition.

A multi-drug resistant HIV-1 protease is resistant to the dimerization inhibitory activity of TLF-PafF.

Human immunodeficiency virus type-1 (HIV-1) protease, a homodimeric aspartyl protease, is a critical drug target in designing anti-retroviral drugs to treat HIV/AIDS. Multidrug-resistant (MDR) clinical isolate-769 HIV-1 protease (PDB ID: 3PJ6) has been shown to exhibit expanded active site cavity with wide-open conformation of flaps (Gly48-Gly52) due to the accumulation of multiple mutations. In this study, an HIV-1 protease dimerization inhibitor (PDI)-TLF-PafF, was evaluated against MDR769 HIV-1 protease using X-ray crystallography. It was hypothesized that co-crystallization of MDR769 HIV-1 protease in complex with TLF-PafF would yield either a monomeric or a disrupted dimeric structure. However, crystal structure of MDR769 I10V HIV-1 protease co-crystallized with TLF-PafF revealed an undisrupted dimeric protease structure (PDB ID: 4NKK) that is comparable to the crystal structure of its corresponding apo-protease (PDB ID: 3PJ6). In order to understand the binding profile of TLF-PafF as a PDI, docking analysis was performed using monomeric protease (prepared from the dimeric crystal structure, PDB ID: 4NKK) as docking receptor. Docking analysis revealed that TLF-PafF binds at the N and C termini (dimerization domain) in a clamp shape for the monomeric wild type receptor but not the MDR769 monomeric receptor. TLF-PafF preferentially showed higher binding affinity to the expanded active site cavity of MDR769 HIV-1 protease than to the termini. Irrespective of binding location, the binding affinity of TLF-PafF against wild type receptor (-6.7kcal/mol) was found to be higher compared to its corresponding binding affinity against MDR receptor (-4.6kcal/mol) suggesting that the MDR769 HIV-1 protease could be resistant to the PDI-activity of TLF-PafF, thus supporting the dimeric crystal structure (PDB ID: 4NKK).

Ruthenium tris(2-pyridylmethyl)amine as an effective photocaging group for nitriles.

Ruthenium(II) tris(2-pyridylmethyl)amine (TPA) is an effective caging group for nitriles that provides high levels of control over the enzyme activity with light. Two caged nitriles were prepared, [Ru(TPA)(MeCN)2](PF6)2 (1) and [Ru(TPA)(3)2](PF6)2 (2), where 3 is the cathepsin K inhibitor Cbz-Leu-NHCH2CN, and characterized by various spectroscopic techniques and mass spectrometry. Both 1 and 2 show the release of a single nitrile within 20 min of irradiation with 365 nm light. Complex 2 acts as a potent, photoactivated inhibitor of human cathepsin K. IC50 values were determined for 2 and 3. Enzyme inhibition for 2 was enhanced by a factor of 89 upon exposure to light, with IC50 values of 63 nM (light) and 5.6 µM (dark).

The mononuclear metal center of type-I dihydroorotase from Aquifex aeolicus.

BACKGROUND: Dihydroorotase (DHO) is a zinc metalloenzyme, although the number of active site zinc ions has been controversial. E. coli DHO was initially thought to have a mononuclear metal center, but the subsequent X-ray structure clearly showed two zinc ions, α and ß, at the catalytic site. Aquifex aeolicus DHO, is a dodecamer comprised of six DHO and six aspartate transcarbamoylase (ATC) subunits. The isolated DHO monomer, which lacks catalytic activity, has an intact α-site and conserved ß-site ligands, but the geometry of the second metal binding site is completely disrupted. However, the putative ß-site is restored when the complex with ATC is formed and DHO activity is regained. Nevertheless, the X-ray structure of the complex revealed a single zinc ion at the active site. The structure of DHO from the pathogenic organism, S. aureus showed that it also has a single active site metal ion. RESULTS: Zinc analysis showed that the enzyme has one zinc/DHO subunit and the addition of excess metal ion did not stimulate catalytic activity, nor alter the kinetic parameters. The metal free apoenzyme was inactive, but the full activity was restored upon the addition of one equivalent of Zn2+ or Co2+. Moreover, deletion of the ß-site by replacing the His180 and His232 with alanine had no effect on catalysis in the presence or absence of excess zinc. The 2.2 Å structure of the double mutant confirmed that the ß-site was eliminated but that the active site remained otherwise intact. CONCLUSIONS: Thus, kinetically competent A. aeolicus DHO has a mononuclear metal center. In contrast, elimination of the putative second metal binding site in amidohydrolyases with a binuclear metal center, resulted in the abolition of catalytic activity. The number of active site metal ions may be a consideration in the design of inhibitors that selectively target either the mononuclear or binuclear enzymes.

Reductive coupling of azides mediated by an iron(II) bis(alkoxide) complex.

The iron(III) hexazene complex (RO)2Fe(µ-κ(2):κ(2)-AdN6Ad)Fe(OR)2 (3) was synthesized via reductive coupling of 1-azidoadamantane at the iron(II) bis(alkoxide) complex Fe(OR)2(THF)2 (2). The X-ray crystal structure depicts electron delocalization within the hexazene moiety. Density functional theory studies propose the formation of an iron azide dimer on the route to hexazene, in which each azide is monoreduced and the iron centers are oxidized to the 3+ oxidation state.

Volatile and thermally stable mid to late transition metal complexes containing α-imino alkoxide ligands, a new strongly reducing coreagent, and thermal atomic layer deposition of Ni, Co, Fe, and Cr metal films.

Treatment of MCl2 (M = Cu, Ni, Co, Fe, Mn, Cr) with 2 equiv of α-imino alkoxide salts K(RR'COCNtBu) (R = Me, tBu; R' = iPr, tBu) afforded M(RR'COCNtBu)2 or [Mn(RR'COCNtBu)2]2 in 9-75% yields. These complexes combine volatility and high thermal stability and have useful atomic layer deposition (ALD) precursor properties. Solution reactions between Ni, Co, and Mn complexes showed that BH3(NHMe2) can reduce all to metal powders. ALD growth of Ni, Co, Fe, and Cr films is demonstrated. Mn film growth may be possible, but the films oxidize completely upon exposure to air.