Exploring CH-activation pathways in bifunctional zirconocene/borane systems

The dimethylsilanediyl-bridged ansa-zirconocene dichloride 1, that contains a pendent allyl substituent at a Cp-ring, adds HB(C(6)F(5))(2) to the vinyl group to yield the bifunctional zirconocene/borane complex 2. Substituted benzimidazoles were added to the strongly electrophilic borane moiety as protective groups, which allowed subsequent chloride versus -CH(2)SiMe(3) exchange at zirconium to take place by treatment with the respective alkyllithium reagent. Alternatively, the introduction of active sigma-ligands at zirconium is carried out first, followed by the hydroboration reaction. This route was followed for the synthesis of the diphenyl-ansa-zirconocene/borane complex 12. Complex 12 reacts slowly in solution by intramolecular electrophilic attack of the borane at its adjacent Cp-ring, followed by deprotonation using a [Zr]-Ph group to yield the zwitterionic complex 14 featuring a borata-tetrahydroindenyl moiety as part of the ansa-metallocene framework. Complex 14 was characterized by X-ray diffraction. It adds PMe(3) at zirconium to yield 15. Thermolysis of 12 with excess PMe(3) leads to the formation of the (aryne)zirconocene complex 18, which is stabilized by PMe(3) coordination to zirconium and PMe(3) addition to boron. N-Methylbenzimidazole adds to the -B(C(6)F(5))(2) unit of 12 to give the 1:1 adduct 19. Thermolysis of 19 at 80 degrees C in benzene solution in the presence of one additional equivalent of N-methylbenzimidazole results in deprotonation of the substrate to yield the sigma-N-methylbenzimidazolyl zirconium complex 20 (as a mixture of two diastereoisomers). An additional N-methylbenzimidazole ligand is bonded to the B(C(6)F(5))(2) unit in this product.     

Chemie der Pleuromutiline, 10. Mitt.: 1,2-Transposition der Carbonylfunktion im Cyclopentanonteil des tricyclischen Gerüstes

2-Hydroxy-19,20-dihydropleuromutilin (10) undergoes a stereospecific ketolisomerisation when treated with base under phase/transfer conditions (11, 12). The subsequent reductive elimination of the 3-acetoxygroup afforded mutilin with a 1,2-transposed ketofunction (13).

     

Die Struktur des Paucins

Zusammenfassung Beim Abbau von Paucin wird Brenzcatechin, Kaffeesäure und Putrescin erhalten. Daraus und aus spektroskopischen Befunden ergibt sich für das Paucin die Strukturformel3.

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The structure of Paucine

Paucine can be degradated to catechol, caffeic acid and putrescine. This together with spectroscopic data allows us to deduce formula3 for paucine.

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Mit 6 Abbildungen

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Meinem Lehrer, Prof. Dr.H. Bretschneider, zum 65. Geburtstag gewidmet.     

Incipience of quantum chaos in the spin-boson model

The peculiar spectral properties of the spinboson model make it suitable for an investigation of quantum nonintegrability effects and level statistics from a new perspective. For fixed spin quantum numbers, its energy spectrum consists of 2s+1 sequences of levels with no upper bound. These sequences are identified and labelled consecutively by means of a quantum invariant calculated from the time average of a non-stationary operator. For integrable cases, level repulsion (on the energy axis) is limited to states within each sequence. From the observed spectral properties, we infer a series ofs-dependent level-spacing distributions. They converge towards a Poisson distribution fors. For nonintegrable cases, level repulsion becomes a universal phenomenon, but the amount of repulsion between two states decreases with increasing separation (in label) of the two sequences to which they belong. For smalls, the quantum nonintegrability effects are compelling but not at all chaotic. Nevertheless, they contain all the ingredients necessary to produce the symptoms commonly described as indicators of quantum chaos. In this model, we can observe quantum chaos in the making under very controllable conditions.     

Exponential weak Bernoulli mixing for collet-eckmann maps

We prove exponential weak Bernoulli mixing for invariant measures of certain piecewise monotone interval maps studied in [BK] and [KN]. In particular we prove this for unimodal maps with negative Schwarzian derivative satisfying lim , wherec is the unique critical point ofT.     

A characterization ofL n(K) as a permutation group

In 1972 M. O'Nan proved thatL _n (q),h 3; can be characterized as a doubly-transitive groupG on a finite set , whereG _a has an Abelian normal subgroup acting not semi-regularly on -a. In the Main Theorem we show that a similar statement holds if is infinite. Our result implies O'Nan's theorem.This paper is part of the author's Ph.D. thesis written under supervision of Prof. F. G. Timmesfeld.     

On the verification of Clark's example of a euclidean but not norm-euclidean number field

In the preceding paper [2], D. Clark proved—modulo a finite amount of computation—that the ring of integersR of admits explicit euclidean algorithms, although it is not euclidean for the norm: In fact, every completely multiplicative function ϕ:R→R _>-0 which sends the prime elements above 23 to a value larger than 25 and which agrees with the absolute norm at all other primes defines a euclidean algorithm forR. The referee had felt that an independent verification of the computer-assisted proofs of Lemmas 1 and 2 of [2] was desirable, and that it should be carried out separately from the refereeing process in the light of the public, conforming to C. Lam's eloquent suggestions [3]. F. Lemmermeyer and the present author succeeded in confirming Clark's result (independently of each other). This note gives some details of the methods employed in the verifications.     

The Four-Connected Net in the CeCu(2) Structure and Its Ternary Derivatives. Its Electronic and Structural Properties

The crystallochemistry of and the bonding in the orthorhombic four-connected nets of BaIn(2) (CeCu(2) structure) and of CaPtSn (TiNiSi structure, a derivative of the CeCu(2) structure) are analyzed with approximate molecular orbital calculations. Following the Zintl concept, in BaIn(2) the In(-) ions are isoelectronic with group IV tin and should adopt a four-connected structure. In contrast to alpha-tin, which has a cubic diamond structure, the indium ions in BaIn(2) build up an orthorhombic three-dimensional four-connected net containing distorted tetrahedra and ladder polymers of four-membered rings. In the CeCu(2) structure (space group Imma) two bond angles in these distorted tetrahedra are fixed at 90 degrees. The four-connected net in the CeCu(2) structure is topologically related to the layers in black phosphorus (space group Cmca). In CaPtSn (TiNiSi structure) the orthorhombic four-connected net is formed by (PtSn)(2)(-) ions in an ordered arrangement. Calculations on BaIn(2) and CaPtSn show that the four-connected nets are increasingly stabilized as the valence electron count is increased from 16 to 30 valence electrons per 4 formula units. For more than 30e, the nets are destabilized due to filling of M-E antibonding states. Structural data obtained by precise single crystal investigations for the TiNiSi series CaPdIn (20e), CaPdSn (24e), CaPdSb (28e), and CaAgSb (32e), confirm the results of the extended Hückel calculations. We find an interesting and understandable angular asymmetry of the tetrahedral sites in these ternary compounds.     

Analysis of Open Discrete Time Queueing Networks: A Refined Decomposition Approach

This paper deals with approximate analysis methods for open queueing networks. External and internal flows from and to the nodes are characterized by renewal processes with discrete time distributions of their interarrival times. Stationary distributions of the waiting time, the queue size and the interdeparture times are obtained using efficient discrete time algorithms for single server (GI/G/1) and multi-server (GI/D/c) nodes with deterministic service. The network analysis is extended to semi-Markovian representations of each flow among the nodes, which include parameters of the autocorrelation function.