Synthesen von Heterocyclen, 85. Mitt.: Über die α-Acyllactonumlagerung von 5-Benzoyl-dehydracetsäure

Zusammenfassung Die vonButt undElvidge aufgefundenen Isomeren, 4-Hydroxy-5-acetyl-6-phenyl-pyron-(2) (1) und 4-Hydroxy-5-ben-zoyl-6-methyl-pyron-(2) (2), ergeben bei der Umsetzung mit POCl₃ und Eisessig 5-Benzoyl-dehydracetsäure (3). Im Gegensatz zur Dehydracetsäure² reagiert 5-Benzoyl-dehydracetsäure (3) in alkohol. HCl zum 2,6-Dimethyl-3-äthoxycarbonyl-5-benzoyl-pyron-(4) (6). Die Struktur dieser Verbindung wird auf chemischem und physikalischem Wege abgeleitet.Mit wäßr. HCl läßt sich3 in 2,6-Dimethyl-5-benzoyl-pyron-(4) (5) umwandeln.

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The isomeric compounds¹ 4-hydroxy-5-acetyl-6-phenyl-pyron-2 (1) and 4-hydroxy-5-benzoyl-6-methyl-pyron-2 (2) yield 5-benzoyl-dehydroacetic acid (3) if with glacial acetic acid and POCl₃. In contrast to dehydroacetic acid² 5-benzoyl-dehydroacetic acid (3) reacts in ethanolic HCl to 2,6-dimethyl-3-carbethoxy-5-benzoyl-pyron-(4) (6).However, with aquenous HCl3 is converted to 2.6-dimethyl-5-benzoyl-pyron-(4) (5).

     

Reaktionen der Cycloheptatrienylkomplexe [η7-C7H7W(CO)3]BF4 und η7-C7H7Mo(CO)2 Br mit Neutralliganden und die elektrochemische Reduktion des Wolframkomplexes

Reactions of the Cycloheptatrienyl Complexes [η⁷-C₇H₇W(CO)₃]BF₄ and η⁷-C₇H₇Mo(CO)₂Br with Neutral Ligands and the Electrochemical Reduction of the Wolfram Complex Compounds of the type [η⁷-C₇H₇M(CO)₂L][BF₄] (L = P(C₆H₅)₃, As(C₆H₅)₃, Sb(C₆H₅)₃ for M = W and L = N₂H₄ for M = Mo) were synthesized and characterisized. The iodide η⁷-C₇H₇W(CO)₂I reacts with the diphosphine ((C₆H₅)₂PCH₂)₂ to give the trihapto complex η³-C₇H₇ W(CO)₂I((C₆H₅)₂PCH₂)₂. In the case of η⁷-C₇H₇Mo(CO)₂ Br reaction with hydrazine leads to the substitution product [η⁷-C₇H₇ Mo(CO)₂N₂H₄]^⊕, which can be stabilized by large anions. The binuclear complex [C₇H₇W(CO)₃]₂ has been synthesized electrochemically.     

Metallcarbonyl-Synthesen,XIV. Neuartige Vanadium-, Niob- und Tantal-Komplexe mit Wasserstoff-Brücken

Syntheses of Metal Carbonyls, XIV. Novel Vanadium, Niobium, and Tantalum Complexes Having Hydrido Bridges The novel homo- and heterodinuclear organometallic μ-hydrido compounds 3a – c of vanadium, niobium, and tantalum have been synthesized by light-induced reactions of the hydridoniobium complex (η⁵-C₅H₅)₂NbH₃ ( 1 ) with the half-sandwich complexes (η⁵-C₅H₅)M(CO)₄ ( 2a : M = V; 2b : M = Nb; 2c : M = Ta). These compounds have the general composition L_xM – H – Nb(CO)(η⁵-C₅H₅)₂. The formation of the M – H – Nb moieties is a dark-reaction preceded by two photoreactions that are independent from each other elimination of CO from 2a – c and elimination of H₂ from 1 , with the extruded carbon monoxide being transfered to the (η⁵-C₅H₅)₂NbH fragment; subsequent fixation of the species (η⁵-C₅H₅)₂Nb(CO)H thus generated to the photogragments (η⁵-C₅H₅)M(CO)₃ results in donor stabilization of these latter groups. The structural architecture of the derivatives 3a und b was established by X-Ray diffraction. The hydrogen bridges are to be considered as three-center two-electron functions that are responsible for a serious lengthening of the otherwise by at least 40 pm shorter metal-to-metal distances amounting to 371.3 pm in 3a and 373.3 pm in 3b (mean values).     

Divergencies in a vector model with hyperbolic symmetry on a chain

A chain of interacting vectors (, ) withn components subject to the hyperbolic conditions ²–²=1 is considered. The interaction possesses a global non-compactO(1, n–1)/O(1)×O(n–1) symmetry. Symmetries of this kind are known from the study of disordered electronic systems. The non-compactness of the symmetry group causes divergencies such that a symmetry breaking term is necessary. Asymptotic behaviour of the expectation values and long-ranged correlation functions are calculated for a small symmetry breaking field.Supported in part by the Deutsche Forschungsgemeinschaft through the Sonderforschungsbereich 123 at the University of Heidelberg     

Density functional calculations of NMR chemical shifts and ESR g-tensors

An overview is given on recent advances of density functional theory (DFT) as applied to the calculation of nuclear magnetic resonance (NMR) chemical shifts and electron spin resonance (ESR) g-tensors. This is a new research area that has seen tremendous progress and success recently; we try to present some of these developments. DFT accounts for correlation effects efficiently. Therefore, it is the only first-principle method that can handle NMR calculations on large systems like transition-metal complexes. Relativistic effects become important for heavier element compounds; here we show how they can be accounted for. The ESR g-tensor is related conceptually to the NMR shielding, and results of g-tensor calculations are presented. DFT has been very successful in its application to magnetic properties, for metal complexes in particular. However, there are still certain shortcomings and limitations, e.g., in the exchange-correlation functional, that are discussed as well. Received: 24 October 1997 / Accepted: 19 December 1997     

Die Molekül- und Kristallstrukturen von (CO)4 W(μ-S-t-C4H9)2W(CO)4, η7-C7H7W(μ-SC6H4CH3)3W(CO)3 und η7-C7H7W(μ-S-n-C4H9)3W(CO)(μ-S-n-C4H9)2W(CO)4

Molecular and Crystal Structures of (CO)₄W(μ-S-t-C₄H₉)₂W(CO)₄, η⁷-C₇H₇W(μ-SC₆H₄CH₃)₃W(CO)₃ and η⁷-C₇H₇W(μ-S-n-C₄H₉)₃W(CO)(μ-S-n-C₄H₉)₂W(CO)₄ The molecular structures of the two binuclear complexes (CO)₄W(μ-S-t-C₄H₉)₂W(CO)₄ and η⁷-C₇H₇W(μ-SC₆H₄CH₃)₃W(CO)₃ and of the tungsten cluster η⁷-C₇H₇W(μ-S-n-C₄H₉)₃W(CO)-(μ-S-n-C₄H₉)₂W(CO)₄ respectively are described. In the nonlinear trinuclear cluster the central tungsten atom is connected to the two tungsten atoms by two and three μ-S-n-C₄H₉ bridges respectively and additionally by one W? W bond each. The coordination sphere of the W atoms is completed by a η⁷-C₇H₇ ring and four CO groups respectively; the central tungsten carries an additional CO group.     

The electronic structures of tetrahedral oxo-complexes. The nature of the “charge transfer” transitions

The electronic structures of MnO^?₄, MnO^2?₄, MnO^3?₄, CrO^2?₄, CrO^3?₄, VO^3?₄, RuO₄, RuO^?₄, RuO^2?₄, TcO^?₄ and MoO^2?₄ have been investigated using the Hartree-Fock-Slater Discrete Variational Method. The calculated ordering of the valence orbitals of all the comlexes is: t₁, 4t₂, 3a₁, 1c, 3t₂, with t₁ the orbital of highest energy. The calculated single transition energies are in good agreement with experimental values and indicate the uniform assignment: t₁ → 2e(v₁), 4t₂ → 2e(v₂). t₁ → 5t₂(v₃), and 4t₂ → 5t₂(v₄). A/D values, calculated from the theory of magnetic circular dichroism (MDC) also support this assignment.Population analyses reveal that all complexes, whether d⁰, d¹ or d², have d-orbital populations close to those of the corresponding M²⁺ ions in which two electrons have been removed from the (n + 1)s orbital of M. This is also true of the excited states, such as t₁ → 2e and 4t₂ → 2e, where a transfer of charge from the ligands to the metal has previously been assumed. It is shown that, instead of a transfer of charge from ligands to metal, electronic excitation consists of a rearrangement of electron density both at the ligands and at the metal.     

High-frequency and -field EPR investigation of a manganese(III) N-confused porphyrin complex, [Mn(NCTPP)(py)2

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.     

Mehrfachbindungen zwischen hauptgruppenelementen und übergangsmetallen: VII. Oxidative decarbonylierungsprozessein der photochemie von tricarbonyl(η5-pentamethylcyclopentadienyl)rhenium: Neue oxo—rhenium-komplexe

Short-wavelength photolysis of tricarbonyl(η⁵-pentamethylcyclopentadienyl)rhenium (1) (λ < 300 nm, quartz-glass) in tetrahydrofuran yields under partial or complete decarbonylation three novel organorhenium compounds, with the relative yields depending upon the irradiation time. Formed by exhaustive oxidative decarbonylation, the complex trioxo(η⁵-pentamethylcyclopentadienyl)rhenium(VII) (5) represents the first example of the new class of oxo half-sandwich complexes. The derivatives (μ-O)[(η⁵-C₅Me₅)Re(CO)₂]₂ (2; Me = CH₃) and (η⁵-C₅Me₅)₂Re₂(CO)₂O₂ (3; Me = CH₃) containing both oxo and carbonyl ligands are formed from 1 at shorter irradiation times. Both compounds are isolable intermediates along the mechanistically not yet fully established sequence 1 → → 5 as they are degraded to 5 under CO₂ elimination in the presence of air and/or light. The mixed oxo carbonyl complex 2 has been characterized by means of single-crystal X-ray diffraction techniques (triclinic, space group P$\text{1}$-C_i¹; a 907.4(2), b 1040.2(3), c 1414.3(4) pm; α 79.99(2), β 88.42(2), γ 66.18(2)°; R_iso = 0.068, R_aniso = 0.037, R_w = 0.031). The molecular structure centres around an isosceles Re₂O triangle whose metal centres exhibit a strongly distorted square-pyramidal geometry; the metal-metal distance recorded at 281.7(1) pm is in agreement with a single bond by the EAN rule. The centrically coordinated, planar five-membered ring ligands are parallel to each other (interplanar angle 2°) and occupy trans-positions with respect to the central Re₂O geometry.