"... and honour their art!" – evaluation of historical and new routes to 1,5-dihydroxy-6-oxo-1,6-dihydropyridine-2-carboxylic acid and 1,3-dihydroxy-2-oxo-3-pyrroline-4-carboxylic acid.

The historical and recent literature describing synthetical pathways to the title compds. is comprehensively summarized and evaluated. Routes via 2,5-dioxoadipic acid or 2,5-dihydroxymuconic acid as intermediates could not be followed reproducibly. 3-Hydroxy-2-oxo-2H-pyran-6-carboxylic acid and Et 3-hydroxy-2-oxo-3-pyrroline-4-carboxylate (I) were fully characterized by spectroscopic methods and single-crystal x-ray diffraction. Both compds. have an enolic structure in soln. as well as in the solid state. A recently published ring-closing metathesis (RCM) protocol to a deriv. of the first title compd. was unproductive in the authors' hands. The authors present a new two-step synthesis of the similarly substituted 5-hydroxy-6-oxo-1,6-dihydropyridine-2-carboxamide (II) using succinyl cyanide. The product was identified and characterized by spectroscopic methods and x-ray crystallog. [on SciFinder(R)

Bulk spin-crossover in the complex [FeL(NCS)(2)] of a tris(pyridyl)ethane-derived N-4-ligand-a temperature-dependent crystallographic study

Dieser Beitrag ist mit Zustimmung des Rechteinhabers aufgrund einer (DFG geförderten) Allianz- bzw. Nationallizenz frei zugänglich.This publication is with permission of the rights owner freely accessible due to an Alliance licence and a national licence (funded by the DFG, German Research Foundation) respectively.We have recently shown that the vacuum-deposited complex [FeIIL(NCS)2] (L: 1-{6-[1,1-di(pyridin-2-yl)ethyl]-pyridin-2-yl}-N,N-dimethylmethanamine) is capable of a thermally induced spin crossover (SCO) in direct contact with a graphite surface. The SCO significantly differs from the transition behaviour in the bulk phase (powder). In the present work, the assumption of virtually no intermolecular interaction in the powder is confirmed by comparison with the spin transition in acetone solution (T1/2 = 234[3] K, ΔT80 = 58[4] K), as monitored by temperature-dependent UV/Vis spectroscopy. The complex crystallises from chlorocarbons in the form of a number of pseudopolymorphs. Amongst these, the sufficiently stable solvate [FeIIL(NCS)2]·CHCl3 is investigated by variable-temperature single-crystal X-ray diffractometry. Its SCO behaviour (T1/2 = 240[3] K, ΔT80 = 35[4] K) correlates with features of molecular structure that are unambiguously identified by analysis of the tensor of thermal expansion. Following comprehensive comparison of spin-transition properties in different states of aggregation (also in relation to the newly synthesised high-spin iron(II) and iron(III) complexes [FeIICl2L] and [FeIIICl2L]PF6), a mode of adsorption on graphite surfaces is proposed, that complies with all previous findings.DFG, SFB 658, Elementarprozesse in molekularen Schaltern auf Oberfläche

3d-and 4d-metal(II) complexes of a tris(pyridyl)ethane-derived N-4 ligand – a structural study and reactivity remarks

A series of complexes of the new N-4 chelate ligand L (L = 1-{6-[1,1-bis(pyridin-2-yl) ethyl] pyridin-2-yl}-N, N-dimethylmethanamine) with intermediate to late divalent transition metal ions M was obtained by the reaction between L and the respective chloride salt or similar precursor in methanol: [MCl2L] (M = Mn, Fe, Co, Ni, Zn; Ru) and [CuClL]Cl. The stereochemical characteristics of the chelate ligand were studied by means of single-crystal X-ray diffraction, and quantified on the basis of several geometric parameters, including the tetragonal distortion Sigma and the continuous symmetry measure S(O-h). The overall distortion of the coordination environment is predomi-nantly determined by the steric demand of the central ion, while electronic or other subtler influences essentially contribute to the distortion of the ligand L. Unlike similar complexes, [(MnCl2L)-Cl-II] cannot be oxidized to a manganese(III) complex by dioxygen, hydrogen peroxide, or iodosylbenzene. In [(RuCl2L)-Cl-II], one chlorido ligand can be exchanged against small p-accepting molecules such as acetonitrile or dinitrogen. L offers an environment ideal for small metal ions (0.4-0.6 angstrom), such as low-spin iron(II), which rationalizes the late onset of thermal spin crossover in the complex [(FeL)-L-II(NCS)(2)].DFG, SFB 658, Elementarprozesse in molekularen Schaltern auf Oberfläche

TFE and Spt4/5 open and close the RNA polymerase clamp during the transcription cycle

Transcription is an intrinsically dynamic process and requires the coordinated interplay of RNA polymerases (RNAPs) with nucleic acids and transcription factors. Classical structural biology techniques have revealed detailed snapshots of a subset of conformational states of the RNAP as they exist in crystals. A detailed view of the conformational space sampled by the RNAP and the molecular mechanisms of the basal transcription factors E (TFE) and Spt4/5 through conformational constraints has remained elusive. We monitored the conformational changes of the flexible clamp of the RNAP by combining a fluorescently labeled recombinant 12-subunit RNAP system with single-molecule FRET measurements. We measured and compared the distances across the DNA binding channel of the archaeal RNAP. Our results show that the transition of the closed to the open initiation complex, which occurs concomitant with DNA melting, is coordinated with an opening of the RNAP clamp that is stimulated by TFE. We show that the clamp in elongation complexes is modulated by the nontemplate strand and by the processivity factor Spt4/5, both of which stimulate transcription processivity. Taken together, our results reveal an intricate network of interactions within transcription complexes between RNAP, transcription factors, and nucleic acids that allosterically modulate the RNAP during the transcription cycle

Tetrapodal amidoxime ligands I. Coordination isomerism due to self-complementary dimerization of a pyramidal cobalt(III) coordination module

Dieser Beitrag ist mit Zustimmung des Rechteinhabers aufgrund einer (DFG geförderten) Allianz- bzw. Nationallizenz frei zugänglich.This publication is with permission of the rights owner freely accessible due to an Alliance licence and a national licence (funded by the DFG, German Research Foundation) respectively.A bis-μ-amidoximato-bridged cobalt(III) dimer obtained with a new tetrapodal ligand possesses interesting structural parameters as a consequence of intramolecular hydrogen bonding intentionally built into the complex. Its synthesis and properties are described. The new ligand type combines attributes of two previously described ligand classes: It binds a metal ion in a tetrapodal pentadentate fashion and forms a pseudomacrocycle through hydrogen bonds, characteristic of chelating oxime ligands. Coordination isomerism, which is a consequence of dimer formation, has been analyzed by means of X-ray crystallography and carbon-13 nuclear magnetic resonance spectroscopy

Carbamoyl Derivatives of a Pyridine-Based Tetraamine

The reaction of four equivalents of phenyl or tert-butyl isocyanate with the pyridine-derived tetraamine 2,6-C3H3N[CMe(CH2NH2)2]2 in toluene gives high yields of the quadruply ureido substituted products 2,6-C5H3N[CMe(CH2R)2]2 [R = -NH(CO)NHPh and -NH(CO)NHtBu]. Full spectroscopic data for both compounds are given. A single crystal X-ray structure determination of the phenyl derivative reveals an intricate network of both intra- and intermolecular hydrogen bonds involving the C=O and both NH functionalities in all ureido groups.DFG, SPP 1118, Sekundäre Wechselwirkungen als Steuerungsprinzip zur gerichteten Funktionalisierung reaktionsträger Substrat

Signal-to-noise ratio of temperature measurement with Cernox sensors at various supply currents

The Karlsruhe Institute of Technology (KIT) has developed a new thermal method for flow measurement, which is particularly suitable for the application in cryogenic systems. In this method, the stability and the resolution of temperature measurement is important, rather than precision. In other words, constant offsets in temperature measurements can be ignored, and the temperature sensors can be operated at supply currents beyond their nominal design value in order to gain resolution. For this application, the performance of two Cernox TM type CX-1050-SD-HT-1.4L sensors was measured in a temperature range between 300 K and 4 K. The experiments were carried out in the calibration cryostat at the Institute for Technical Physics. Sensors were connected to a Lake Shore Model 121 current source and a Keithley 2701/E digital multimeter for voltage measurements. At constant calibration temperatures, the supply currents were varied such that the resulting voltage drops lay in-between 10 mV and 100 mV. The influence on both the noise and the temperature offset are presented

Bond activation in iron(II) and nickel(II) complexes of polypodal phosphanes

A pyridine-derived tetraphosphane ligand (donor set: NP4) has been found to undergo remarkably specific C-P bond cleavage reactions, thereby producing a ligand with an NP3 donor set. The reaction may be reversed under suitable conditions, with regeneration of the original NP4 ligand. In order to investigate the mechanism of this reaction, the NP3 donor ligand C5H3N[CMe(CH2PMe2)2][CMe2(CH2PMe2)] (11) was prepd., and its iron(II) complex 4 generated from Fe(BF4)2·6 H2O, with Me diethylphosphinite (7) as an addnl. monodentate ligand. Ligand 11 has, in addn. to the NP3 donor set, one Me group in close contact with the iron center, reminiscent of an agostic M···H-C interaction. Depending on the stoichiometric amt. of iron(II) salt, a side product 15 is formed, which has a diethylphosphane ligand instead of the phosphinite 7 coordinated to iron(II). While attempts to deprotonate the metal-coordinated Me group in 4 were unsuccessful, the reaction was shown to occur in an alternative complex (18), which is similar to 4 but has a trimethylphosphane ligand instead of the phosphinite 7. The reaction of complex 15 with CO gave two different products, which were both characterized by single-crystal X-ray diffraction. One (19) is the dicarbonyl iron(II) complex of the triphosphane ligand 11, the other (3) is the carbonyl iron(II) complex of the tetraphosphane C5H3N[CMe(CH2PMe2)2]2 (1). This suggests an intermol. mechanism for the C-P bond formation in question. [on SciFinder(R)

O−O Bond Formation and Liberation of Dioxygen Mediated by N5‐Coordinate Non‐Heme Iron(IV) Complexes

Formation of the O−O bond is considered the critical step in oxidative water cleavage to produce dioxygen. High‐valent metal complexes with terminal oxo (oxido) ligands are commonly regarded as instrumental for oxygen evolution, but direct experimental evidence is lacking. Herein, we describe the formation of the O−O bond in solution, from non‐heme, N5‐coordinate oxoiron(IV) species. Oxygen evolution from oxoiron(IV) is instantaneous once meta‐chloroperbenzoic acid is administered in excess. Oxygen‐isotope labeling reveals two sources of dioxygen, pointing to mechanistic branching between HAT (hydrogen atom transfer)‐initiated free‐radical pathways of the peroxides, which are typical of catalase‐like reactivity, and iron‐borne O−O coupling, which is unprecedented for non‐heme/peroxide systems. Interpretation in terms of [FeIV(O)] and [FeV(O)] being the resting and active principles of the O−O coupling, respectively, concurs with fundamental mechanistic ideas of (electro‐) chemical O−O coupling in water oxidation catalysis (WOC), indicating that central mechanistic motifs of WOC can be mimicked in a catalase/peroxidase setting.DFG, 12489635, SFB 658: Elementarprozesse in molekularen Schaltern auf OberflächenTU Berlin, Open-Access-Mittel - 201