Exploring the Intricacies of Weak Interactions in Metal-Metal Bonds Using an Unsymmetrical Carbonyl Precursor and a Triple-Bonded W2(6+) Paddlewheel.

Stepwise reaction of W(CO)6 with tetramethylated bicyclic guanidinate ligands, characterized by a central C(N)3 unit joining two fused six-membered rings with CH2CMe2CH2 units spanning two of the nitrogen atoms, allowed isolation of W2(µ-CO)2(µ-TMhpp)2(η(2)-TMhpp)2, 1, a precursor of W2(TMhpp)4Cl2 ( J. Am. Chem. Soc. 2013 , 135 , 17889 ; TMhpp = [(CH2CMe2CH2)2(C(N)3)]). Subsequent heating of 1 followed by reaction with TlPF6 generates [W2(TMhpp)4](PF6)2, 2. Compound 1 has an edge-sharing bioctahedral (ESBO) arrangement with a W2(µ-CO)2(4+) core having semibridging carbonyl groups, while 2 has a paddlewheel structure with a W2(6+) core spanned by four tetramethyl-substituted bicyclic guanidinate ligands. This compound also has hexafluorophosphate anions along the metal-metal bond that are nestled within methylene groups with the aid of a network of weak C-H···F interactions that prevent a close approach of the fluorine atoms to the dimetal unit. Theoretical computations were carried out on ditungsten model complexes supported by three ligand sets: bicyclic guanidinate, guanidinate, and formamidinate. The computations show that the π-accepting ability of the carbonyl groups significantly lowers the energy of the σ* orbital, and thus, the energy falls below that of the δ orbital. This information along with the diamagnetism of both 1 and 2-as shown by the sharp signals in the (1)H NMR spectra that support a lack of unpaired electrons (S = 0)-is consistent with the electronic configuration of σ(2)π(2)σ*(2)δ(2) (π(2)δ(2)) and thus a formal bond order of 2 for 1 and σ(2)π(4) for the triple-bonded W2(6+) core in 2. A comparison of the W-W bond lengths in 2, its chloro precursor W2(TMhpp)4Cl2, and the corresponding analogue W2(hpp)4Cl2 shows a substantial effect from the axially coordinated ligand, distal lone pair in determining the length of the metal-metal bond for these paddlewheel species. The importance of the ligands in tuning the energy level of the metal-metal bonds that may lead to dramatic changes in physical properties is also discussed. It is noteworthy that bicyclic guanidinates with the strongest π-donating ability push upward the energy level of the δ orbital, thus allowing the compounds to be easily oxidized.

Manipulating magnetism: Ru25⁺ paddlewheels devoid of axial interactions.

Variable-temperature magnetic and structural data of two pairs of diruthenium isomers, one pair having an axial ligand and the formula Ru2(DArF)4Cl (where DArF is the anion of a diarylformamidine isomer and Ar = p-anisyl or m-anisyl) and the other one being essentially identical but devoid of axial ligands and having the formula [Ru2(DArF)4]BF4, show that the axial ligand has a significant effect on the electronic structure of the diruthenium unit. Variable temperature crystallographic and magnetic data as well as density functional theory calculations unequivocally demonstrate the occurrence of π interactions between the p orbitals of the chlorine ligand and the π* orbitals in the Ru2(5+) units. The magnetic and structural data are consistent with the existence of combined ligand σ/metal σ and ligand pπ/metal-dπ interactions. Electron paramagnetic resonance data show unambiguously that the unpaired electrons are in metal-based molecular orbitals.

Fitting the pieces of the puzzle: the δ bond.

The development of our understanding of the δ bond and its role in quadruple metal-metal bonding is described in terms of the conceptual advances and experimental and theoretical results achieved through a 50-year period beginning with the seminal report by Cotton and co-workers in 1964. The work behind the original discovery is described, along with the qualitative orbital description of the components of the quadruple bond. The effect of torsion about the metal-metal axis on the metal-metal bond length is described, together with the conclusion that this accords with a progressive loss of the δ component of the metal-metal bond. The important role of photoelectron spectroscopy in characterizing the loss of electrons from the metal-metal bonding orbitals is reviewed, as are the electron paramagnetic resonance results that establish that unpaired electrons, when present, populate metal-based orbitals. Other important results are described: destabilization of the metal-metal bond to produce strong reducing agents, exceptions to the expected orbital ordering, and the use of chiroptical properties to reveal additional information about the electronic structure of the metal-metal bond.

A strong metal-to-metal interaction in an edge-sharing bioctahedral compound that leads to a very short tungsten-tungsten double bond.

An ionic edge-sharing bioctahedral (ESBO) species has been prepared having a tetramethylated bicyclic guanidinate with two fused six-membered rings characterized by a fairly flat N-C(N)-N skeleton and abbreviated as TMhpp. The anion has two W(IV) atoms bridged by two oxo groups; the metal atoms are also spanned by two bridging guanidinate ligands, and each has two monodentate chlorine atoms. The complex formulated as (H2TMhpp)2[W(µ-O)(µ-TMhpp)Cl2]2 has the shortest W-W distance (2.3318(8) Å) of any species with a σ(2)π(2) electronic configuration. The anion and cations are connected by hydrogen bonds. To unambiguously ascertain the existence of the double-bonded W2(µ-O)2 entity, density functional theory calculations and natural bond orbital analyses were done on an analogous but hypothetical species with a W2(µ-OH)2 core having trivalent tungsten atoms and a possible σ(2)π(2)δ(2) electronic configuration. The calculations decidedly support the presence of tungsten-oxo instead of tungsten-hydroxo groups and thus the existence of the double-bonded W2(µ-O)2 core. The strong bonding interaction between metal atoms is a clear indication that under certain circumstances the two octahedra in ESBO species do not behave as the sum of two mononuclear compounds.

Solubilizing the most easily ionized molecules and generating powerful reducing agents.

Two very soluble compounds having W2(bicyclic guanidinate)4 paddlewheel structures show record low ionization energies (onsets at 3.4 to 3.5 eV) and very negative oxidation potentials in THF (-1.84 to -1.90 V vs Ag/AgCl). DFT computations show the correlation from the gas-phase ionization energies to the solution redox potentials and chemical behavior. These compounds are thermally stable and easy to synthesize in high yields and good purity. They are very reactive and potentially useful stoichiometric reducing agents in nonpolar, nonprotonated solvents.

Direct evidence from electron paramagnetic resonance for additional configurations in uncommon paddlewheel Re2(7+) units surrounded by an unsymmetrical bicyclic guanidinate.

Three rare compounds have been synthesized and structurally characterized; these species have paddlewheel structures and Re(2)(7+) cores surrounded by four bicyclic guanidinates and two axial ligands along the Re-Re axis. Each possesses a formal bond order of 3.5 and a σ(2)π(4)δ(1) electronic configuration that entails the presence of one unpaired electron for each compound. The guanidinate ligands characterized by having CH(2) entities and a central C(N)(3) unit that joins two cyclic units--one having two fused 6-membered rings (hpp) and the other having a 5- and a 6-membered ring fused together (tbn)--allowed the isolation of [Re(2)(tbn)(4)Cl(2)]PF(6), 1, [Re(2)(tbn)(4)Cl(2)]Cl, 2, and [Re(2)(hpp)(4)(O(3)SCF(3))(2)](O(3)SCF(3)), 3. Because of the larger bite angle of the tbn relative to the hpp ligand, the Re-Re bond distances in 1 and 2 (2.2691(14) and 2.2589(14) Å, respectively) are much longer than that in 3 (2.1804(8) Å). Importantly, electron paramagnetic resonance (EPR) studies at both X-band (~9.4 GHz) and W-band (112 GHz) in the solid and in frozen solution show unusually low g-values (~1.75) and the absence of zero-field splitting, providing direct evidence for the presence of one metal-based unpaired electron for both 1 and 3. These spectroscopic data suggest that the unsymmetrical 5-/6-membered ligand leads to the formation of isomers, as shown by significantly broader EPR signals for 1 than for 3, even though both compounds possess what appears to be similar ideal crystallographic axial symmetry on the X-ray time scale.

Experimental and theoretical evidence of aromatic behavior in heterobenzene-like molecules with metal-metal multiple bonds.

Binding two quadruply bonded dimolybdenum units [Mo(2)(DAniF)(3)](+) (DAniF=N,N'-di-p-anisylformamidinate) with two chalcogen atoms generated two molecules with a central core composed of a cyclic six-membered [Mo(2)](2)(µ-EH)(2) species (E=S in 1 and O in 3, and [Mo(2)] is a quadruple-bonded [Mo(2)(formamidinate)(3)] unit). Aerobic oxidation of 1 and 3 followed by concomitant deprotonation gave rise to the corresponding [Mo(2)](2)(µ-E)(2) compounds 2 and 4. The latter show a striking coplanarity and near-bond equalization of the Mo/E cluster. The oxidized species 2 and 4 are diamagnetic in the measured temperature range of 5 to 300 K, which is somewhat unexpected for molecules that have dimetal units with a σ(2)π(4)δ(1) electronic configuration. This suggests there are strong interactions between the dimolybdenum units through the E atoms. The large electronic delocalization of the δ electrons over the entire Mo/E core is supported by the exceptionally large potential separation for the two successive one-electron reductions of the linked Mo(2)(5+) units from the oxidized species (ΔE(½)=1.7 V for the sulfur analogue). This large electronic delocalization has an important effect on the NMR spectroscopic signals for the two sets of methine (N-(CH)-N) protons from the DAniF ligands. Those essentially parallel to the core, H(∥), and those essentially perpendicular to the core, H(⊥), exhibit downfield and upfield chemical shifts, respectively, that are separated by δ=1.32 ppm. The structural, electronic, magnetic, and chemical behaviors for 2 and 4 are consistent with aromaticity, with the [Mo(2)E(2)Mo(2)] cores that resemble the prototypical benzene molecule. Theoretical studies, including DFT calculations, natural bond orbital (NBO) analyses, and gauge-independent atomic orbital (GIAO) NMR spectroscopic calculations, are also consistent with the aromaticity of the [Mo(2)](2)(µ-E)(2) units being promoted by d(δ)(Mo(2))-p(π)(E) π conjugation. The cyclic π conjugation of the central moiety in 2 and 4 involves a total of six electrons with 2e from δ(Mo(2)) and 4e from p(π)(E) orbitals, thereby conforming to Hückel's rule when electrons in the MOs with δ character are considered part of the delocalized system.

Tuning the electrochemistry of Re2(6+) species with divergent bicyclic guanidinate ligands and by modification of axial π interactions.

Four Re(2)(6+) paddlewheel compounds with equatorial bicyclic guanidinate ligands and two monodentate anions in axial positions show a large change in the metal-metal distance that depends on the bite angle of the ligands and whether there are pi interactions between the dimetal unit and the axial ligands. These processes are accompanied by significant changes in the redox behavior. The two pairs of compounds that have been synthesized are Re(2)(tbn)(4)Cl(2), 1, and Re(2)(tbn)(4)(SO(3)CF(3))(2), 2, as well as Re(2)(tbo)(4)Cl(2), 3, and Re(2)(tbo)(4)(SO(3)CF(3))(2), 4, where tbn is the anion of a bicyclic guanidinate with six- and five-membered rings (1,5,7-triazabicyclo[4.3.0]non-6-ene) and tbo is an analogous species with two five-membered rings (the anion of 1,4,6-triazabicyclo[3.3.0]oct-4-ene). For both 1 and 2 as well as for 3 and 4, the metal-metal distances are shorter for the triflate species than for the chloride analogues because of the π interactions of the Cl with the π bonds of the triply bonded Re(2)(6+) cores compounded by a small but symmetry allowed interaction between the antisymmetric combination of the filled σp orbitals of the chlorine atom and the empty σ* orbital of the metal atoms. In addition there is a significant increase in the Re-Re distance from that in the six/five tbn-membered ring to the five/five-membered tbo species. Electrochemical measurements show two redox processes for each set of compounds corresponding to the uncommon Re(2)(6+) → Re(2)(7+) and Re(2)(7+) → Re(2)(8+) processes, which are strongly affected by the bite angle of the guanidinate ligand as well as the ability of the axial ligands to interact with the π orbitals of the dirhenium unit. For 1 and 3, the first redox couples are at 0.146 and 0.487 V, respectively, while for 2 and 4 these are at 0.430 and 0.698 V, respectively.

Nature of bonding in complexes containing "supershort" metal-metal bonds. raman and theoretical study of M2(dmp)4 [M = Cr (natural abundance Cr, 50Cr, and 54Cr) and Mo; dmp = 2,6-dimethoxyphenyl].

We report an investigation of complexes of the type M(2)(dmp)(4) (M = Mo, Cr; dmp = 2,6-dimethoxyphenyl) using resonance Raman (RR) spectroscopy, Cr isotopic substitution, and density functional theory (DFT) calculations. Assignment of the Mo-Mo stretching vibration in the Mo(2) species is straightforward, as evidenced by a single resonance-enhanced band at 424 cm(-1), consistent with an essentially unmixed metal-metal stretch, and overtones of this vibration. On the other hand, the Cr(2) congener has no obvious metal-metal stretching mode near 650-700 cm(-1), where empirical predictions based on the Cr-Cr distance as well as DFT calculations suggest that this vibration should appear if unmixed. Instead, three bands are observed at 345, 363, and 387 cm(-1) that (a) have relative RR intensities that are sensitive to the Raman excitation frequency, (b) exhibit overtones and combinations in the RR spectra, and (c) shift in frequency upon isotopic substitution ((50)Cr and (54)Cr). DFT calculations are used to model the vibrational data for the Mo(2) and Cr(2) systems. Both the DFT results and empirical predictions are in good agreement with experimental observations in the Mo(2) complex, but both, while mutually consistent, differ radically from experiment in the Cr(2) complex. Our experimental and theoretical results, especially the Cr isotope shifts, clearly demonstrate that the potential energy of the Cr-Cr stretching coordinate is distributed among several normal modes having both Cr-Cr and Cr-ligand character. The general significance of these results in interpreting spectroscopic observations in terms of the nature of metal-metal multiple bonding is discussed.

Large changes in electronic structures of Ru2(6+) species caused by the variations of the bite angle of guanidinate ligands: tuning magnetic behavior.

Syntheses and characterization of two Ru(2)(6+) paddlewheel compounds having very different magnetic behavior are reported. The compounds Ru(2)(tbn)(4)Cl(2), 1, and Ru(2)(tbo)(4)Cl(2), 2 (where tbn = the anion of 1,5,7-triazabicyclo[4.3.0]non-6-ene and tbo = the anion of 1,4,6-triazabicyclo[3.3.0]oct-4-ene), have four equatorial bicyclic guanidinate ligands and two chloride ions in axial positions. They show large disparity in Ru-Ru distances of about 0.11 A (2.389(3) and 2.499(3) A at 30 K for 1 and 2, respectively) that is attributed to the divergence in the bite angle of the ligand. Variable temperature structural data show no significant changes in the Ru-Ru distances between 30 and 213 K suggesting that the electronic structure remains unchanged in this temperature range for both compounds. Magnetic studies of 1 indicate there are two unpaired electrons at room temperature but the compound behaves as essentially diamagnetic at approximately 2 K. Compound 2 is non-magnetic across all temperatures in the range of 2 to 300 K. Density functional theory calculations suggest a pi(4)pi*(4)delta(2) electronic configuration for 2, while the magnetic behavior and structural data for 1 are consistent with a sigma(2)pi(4)delta(2)pi*(2) electronic configuration. This shows the importance of the ligand bite angle in determining the electronic configuration of the diruthenium unit and a way to tune magnetic behavior.

Proof by EPR spectroscopy that the unpaired electron in an Os(2)(7+) species is in a delta* metal-based molecular orbital.

Variable temperature structural and EPR studies are reported on the paddlewheel compound [Os(2)(hpp)(4)Cl(2)]PF(6), 1, (hpp = the anion of the bicyclic guanidine 1,3,4,6,7,8-hexahydro-2H-pyrimido[1,2-a]pyrimidine) that contains a rare M(2)(7+) species, with the goal of determining whether the unpaired electron resides in a metal- or ligand-based molecular orbital. Crystallographic studies show that the Os-Os distance in 1 remains essentially unchanged from 213 to 30 K, which is consistent with no changes in electronic structure in this range of temperature. It is noteworthy that the metal-metal distance in 1 is about 0.05 A shorter than that in the precursor Os(2)(hpp)(4)Cl(2), which is consistent with the loss of an electron in a delta* orbital. EPR spectra of 1 were measured in dilute frozen solution, powder, and single crystals. The spectra were observable only below about 50 K, with an exceptionally large line width, approximately 3,750 gauss, for a powdered sample, due to dipolar interactions and to short relaxation times. There is a very small average g value of approximately 0.750 and a cylindrical symmetry about the Os-Os bond. These data are consistent with the unpaired electron orbital having a large L value, such as that of a delta* orbital. The combination of X-ray structural data, the short relaxation time, and the magnetic data provide strong evidence that the unpaired electron in this nine-electron Os(2)(7+) species is localized in a metal-based orbital with this electron residing predominantly in a delta* orbital rather than in a pi* orbital and, thus, having an electronic configuration of sigma(2)pi(4)delta(2)delta*.

Effects of weak intermolecular interactions on the molecular isomerism of tricobalt metal chains.

Depending on the number of interstitial solvent molecules, n, crystals of the linear chain compound Co(3)(dipyridylamide)(4)Cl(2) x nCH(2)Cl(2) adopt either symmetrical or unsymmetrical metal chain structures. We explore here the possible reasons for such behavior using Hirshfeld surface analysis of intermolecular interactions as well as the charge density determined from 100(1) K X-ray diffraction data on the unsymmetrical complex Co(3)(dipyridylamide)(4)Cl(2) x 2.11 CH(2)Cl(2), u-1, and crystal structures of u-1 determined from single crystal synchrotron X-ray diffraction data at 20, 150, and 300 K. The new crystal structures are compared with previous structural results on a crystal with slightly different solvent content. This change in solvent content only affects the bond distances to atom Co(3), which are also strongly affected by temperature changes due to a spin crossover transition. Large differences in intermolecular interactions are revealed by the Hirshfeld surface analysis between symmetrical (s-1) and unsymmetrical (u-1) crystal solvates, suggesting that the molecular isomerism is strongly influenced by crystal packing effects. Topological analysis of the static electron density of u-1 suggests that there is direct metal-metal bonding for both the shorter Co(1)-Co(2) and the longer Co(2)-Co(3) contact. The approximate description of the system as a (Co(2))(2+)-dimer and an isolated Co(2+)-ion is reflected in the character of the metal-ligand interactions, which are more ionic for the isolated Co(3) atom, and the topological charges Co(1)(+0.50), Co(2)(+0.77), and Co(3)(+1.36). The two termini of u-1 are found to be very different, both in terms of structural surroundings as well as topology. The central Co(2) atom is similar to a cobalt atom in a tetragonally distorted octahedral environment resulting in preferred occupancy in the t(2g) orbitals. The Co(1) atom has significant deformation in the xz and yz planes (z along the chain axis, x and y toward ligands) reflecting covalent interactions with the terminal chlorine atom Cl(1). The Co(3) atom has a relatively high occupancy of the d(x(2)-y(2)) orbital and a relatively low occupancy of the d(xy) orbital confirming that these orbitals are involved in the spin crossover process and predominantly responsible for the observed variation in bond lengths with temperature.

Integrin and matrix metalloproteinase expression in human carotid plaque.

BACKGROUND: Neointimal thickening is the major cause of restenosis after carotid endarterectomy (CEA) and carotid stenting. The biologic behavior of these lesions is regulated by the interaction between smooth muscle cells (SMCs), endothelial cells (ECs), and extracellular matrix (ECM) proteins. Although the contribution of the cellular components of neointimal lesions has been extensively studied, the role of the ECM proteins in lesion remodeling is less well defined. METHODS: We examined primary and restenotic carotid endarterectomy specimens to determine their cellular morphology. Tissue was also preserved for protein extraction for Western immunoblotting and mRNA for RT-PCR and cDNA microarray analysis. RESULTS: All primary lesions demonstrated the features of complex atherosclerotic plaque. Restenotic lesions were composed of SMCs embedded in ECM. Microarray analysis demonstrated altered expression of 13 of 96 genes. Eight genes were increased more than 3-fold and five genes were decreased more than 3-fold in primary plaque compared with restenotic lesions. RT-PCR confirmed alpha2-, alpha6-, and beta3-integrin gene expression in reference tissue, primary plaque, and restenotic lesions, with the greatest expression in primary plaque. Primary plaque demonstrated increased protein expression of plasminogen activator inhibitor-1 (PAI-1) and tissue inhibitor of metalloproteinase (TIMP-1). By zymography, pro-MMP-2, pro-MMP-9 levels, and MMP-2 activity were also increased in primary plaque compared with reference and restenotic tissues. CONCLUSIONS: The decreased integrin expression and protease activity in restenotic lesions versus primary carotid plaques suggests that the neointimal lesions were in a quiescent phase. These alterations in protein expression and protease activity demonstrate the importance of proteinase/inhibitor imbalance in regulating plaque remodeling.

Influence of bonding mode of the linkers in the electronic communication of molecular pairs having dimolybdenum units linked by pseudohalides.

Depending on conditions the reactions of [Mo(2)(cis-DAniF)(2)(NCCH(3))(4)](BF(4))(2) (DAniF = N,N'-di-p-anisylformamidinate) with solutions containing thiocyanate anions lead to two compounds: a quadruple-bonded dinuclear species 1, (Bu(n)(4)N)(2)[Mo(2)(cis-DAniF)(2)(NCS)(4)], and a molecular pair 3, [Mo(2)(cis-DAniF)(2)](2)(mu(1,3)-NCS)(4). The latter has a cuboidal structure having two (cis-DAniF)(2)Mo(2)(2+) units, [Mo(2)], with four thiocyanate groups bridging two [Mo(2)] units in an end-to-end fashion in which the N and S atoms serve as the bridging units. On the contrary, the structure of the cyanate isomer, [Mo(2)(cis-DAniF)(2)](2)(mu(1,1)-NCO)(4) (2), shows an end-on binding of the cyanate linkers. Various physical measurements of 2 and its oxidized species 2.PF(6) indicate that there is strong electronic communication between the two dimetal cores. For 1, two reversible oxidation processes were observed in the cyclic voltammogram corresponding to the successive oxidation to 1(+) and an uncommon 1(2+) species that has a triple-bonded Mo(2)(6+) core. DFT calculations indicate that the antibonding character between the Mo-Mo delta orbitals and thiocyanate p orbitals plays a very important role in elevating the HOMO delta orbital energy that allows formation of the dication. A selenium isomer of 3 was also studied. In both the thiocyanate and selenocyanate bridged dimers of dimers, in which the pseudohalide bridges bind the two dimetal units in an end-to-end fashion, long separations between the dimetal units are observed, and these generate very weak electronic interactions.

Evidence of disruption of conjugation involving delta bonds in intramolecular electronic coupling.

A dimer of dimers containing two quadruply bonded [Mo(2)(DAniF)(3)](+) units (DAniF = N,N'-di(p-anisyl)formamidinate) linked by the S-donor linker, dimethyldithiooxamidate was synthesized, structurally characterized, and electronic communication was probed. The core of [Mo(2)(DAniF)(3)](2)(C(2)S(2)N(2)Me(2)), 1, formed by the Mo(2)NSC(2)SNMo(2) atoms shows two fused but non planar six-membered rings, which differs from that of the beta form of dimethyloxamidate analogue that has a heteronaphthalene-type structure (Cotton, F. A.; Liu, C. Y.; Murillo, C. A.; Villagran, D.; Wang, X. J. Am. Chem. Soc. 2004, 126, 14822). For these two analogous compounds electronic coupling between the two [Mo(2)] units, as determined by electrochemical measurements, diminishes considerably upon replacement of O-donor by S-donor atoms (DeltaE(1/2) = 531 mV and 440 mV, respectively). This suggests that the non planar conformation of the linker in 1 hampers a pathway leading to pi conjugation. Density functional theory (DFT) calculations show that the highest occupied molecular orbitals HOMO-HOMO-1 energy gap of 0.12 eV for 1 is much smaller than that of 0.61 eV for the O-donor analogue, which is consistent with the electrochemical data.

An iron complex with an unsupported Fe-Fe bond.

Full metal bonding: The reduction of a six-coordinate, mononuclear Werner-type iron(II) complex (see scheme) resulted in the isolation of a compound with an extraordinarily rare, unsupported Fe-Fe bond having an experimental Fe-Fe distance of 2.6869(6) A and a calculated bond order of 0.5.

Exceptionally strong electronic coupling between [Mo2] units linked by substituted dianionic quinones.

Ligands derived from N-CH(3) substituted benzoquinonemonoimines are exceedingly good facilitators of electronic communication between two quadruply bonded dimolybdenum units and provide record values for comproportionation constants.

Tetra-kis(1,3,4,6,7,8-hexa-hydro-2H-pyrimido[1,2-a]pyrimidin-9-ido-κN,N)niobium(V) hexa-fluorido-phosphate.

The title complex, [Nb(C(7)H(12)N(3))(4)]PF(6), features chelating hpp anions (hpp is 1,3,4,6,7,8-hexahydro-2H-pyrimido[1,2-a]pyrim-idine) that define a distorted dodeca-hedral coordination geometry based on an N(8) donor set. The Nb atom is situated on a site of symmetry , and the PF(6) (-) anion has crystallographic fourfold symmetry.

Photoelectron spectroscopy and DFT calculations of easily ionized quadruply bonded Mo2(4+) compounds and their bicyclic guanidinate precursors.

A series of five bicyclic guanidinate compounds containing various combinations of five- and six-membered rings and substituted alkyl groups have been shown by photoelectron spectroscopy to be easily ionized, with the one having two six-membered rings and four ethyl groups being the most easily ionized. The corresponding anions are capable of forming paddlewheel compounds having quadruply bonded Mo2(4+) units which are also easy to ionize. The most easily ionized compound is the ethyl-substituted Mo2(TEhpp)4 complex which has a broad first ionization band centered around 4.27 +/- 0.03 eV and an ionization onset at the very low energy of 3.93 +/- 0.03 eV. Even the compound with ligands containing two five-membered rings, which favors a long Mo-Mo separation because of the large ligand bite, has an ionization energy (4.78 eV) that is less than those of well-known organometallic reducing agents such as (eta5-C9Me7)2Co and (eta5-C5Me5)2Cr.

El uso del lisímetro de pesada en clavel (Dianthus caryophyllus L.) genera ahorro en fertirriego / The use of the weighing lysimeter in carnation (Dianthus caryophyllus L.) generates saving in fertigation

RESUMEN El exceso o déficit en el volumen de fertirriego genera desbalances nutricionales, en razón a que influyen en el pH y la CE, afectando el desempeño de las plantas. Además, el descontrol del volumen de fertirriego puede causar excesos de lixiviados con efectos perjudiciales en el medioambiente. La fertirrigación en la producción de clavel en la Sabana de Bogotá, se hace de forma empiríca, por tanto, es indispensable ajustar el volumen de fertirriego a las necesidades del cultivo, para evitar los problemas mencionados. Por esta razón, se evaluó el efecto del control del volumen de fertirriego con lisímetro de peasada, en comparación con el manejo del fertirriego tradicional, en el desempeño de las plantas de miniclavel, sembradas en sutrato, en condiciones de invernadero. Para la evaluación, se realizó un diseño experimental en bloques completos al azar, con los tratamientos de sistema de cultivo con lisímetro (CL) y sistema de cultivo con fertirriego tradicional sin lisímetro (SL). Las variables evaluadas fueron volumen de riego, contenido nutricional de planta completa en cinco estadios fenológicos, pH y nutrientes mayores y secundarios (Ca-Mg), en el sustrato y en la solución drenada. El CL genera un ahorro en el volumen de fertirriego en comparación con el SL. Se encontraron diferencias en el continuo planta - sustrato - lixiviado, en N, K, Mg, así como en el pH del sustrato. El CL fue más eficiente, al generar mayor acumulación de masa seca, con el uso de menos agua y nutrientes, sin afectar el rendimiento, ni la calidad.

ABSTRACT The amount of fertigation excess or deficit generates nutritional unbalances given it affects pH, CE, and the nutrients balance influencing the plant development performance. In addition, the uncontrolled fertigation volume can cause an excess of leachates with detrimental effects on the environment. The Fertigation in carnation production in the Bogotá savanna is done empirically, therefore, it is essential to adjust the fertigation volume to the needs of the crop to avoid the mentioned problems. For this reason, the effect of the control of the fertigation volume with weighting lysimeters was evaluated in comparison with the management of traditional fertigation in the performance of the spray carnation plants sown in substrate under greenhouse conditions. For the evaluation, an experimental design was carried out in complete randomized blocks with a lysimeter crop system (LCS) and a traditional crop system without a lysimeter (WLS) as treatments. Irrigation volume, whole plant nutritional content in five phenological stages, pH, primary and secondary (Ca - Mg) nutrients in the substrate, and drainage solution were the variables evaluated. The LCS generates saving in the use of fertigation compared with WLS. Differences were found in the continuum plant - substrate - leached in N, K, Mg, as well as in the pH of the substrate. The LCS treatment was more efficient by generating greater dry mass accumulation, with the use of less water and nutrients without affecting the yield or quality.