Γ-Lakton-cis-anellierung an Δ2- und Δ3- Cholesten

γ-Lactone-cis-annulation to Δ²- and Δ³- Cholestene. From Δ²- and Δ³- cholestene the γ-lactones 11a , 11b , 12a , and 12b are synthesized through the dibromocarbene adducts 3 and 4 , the bromohydrines 5 and 6 , the oxapiropentanes 7 and 8 , and the cyclobutanones 9a , 9b and 10a , 10b , respectively. The ¹³C-NMR.-spectra of 1–8 and 11 as well as the ORD.-spectra of the cyclobutanones 9 and 10 are reported.     

Zur Elektronenstruktur metallorganischer Komplexe der f‐Elemente. 64 Äußert sich die zwitterionische Natur des Triphenylphosphanoxid‐Liganden auch in seinen spektrochemischen Eigenschaften?

Electronic Structures of Organometallic Compounds of f Elements. 64 Does the Zwitterionic Nature of the Triphenylphosphine Oxide Ligand Manifest itself in its Spectrochemical Properties? The triphenylphosphine oxide mono adducts of the moiety tris(η⁵‐cyclopentadienyl)lanthanide(III) (Ln(Cp)₃; Ln = Pr ( 1 ), La ( 2 )) were synthesized and structurally characterized. The Ln–O distances of these compounds are noticeably shorter than those of the corresponding THF adducts. A crystal field (CF) analysis of the optical spectra of 1 leads to a low absolute value of the quadratic CF parameter which is comparable with those of [Pr(Cp)₃(L)]^? adducts with anionic bases but not with [Pr(Cp)₃(MeTHF)]. Reasons for the latter finding are presented.     

Syntheses and Structures of Heterometallic Fe–Ta Chalcogenido Clusters

Two Fe–Ta containing sulfido complexes were prepared by the reaction of the metal halide salts with bis-trimethylsilylsulfide in the presence of PMe₃. The complexes demonstrate that coordination chemistry with iron sulfides can give access to a range of heterometallic complexes. In [Cl(Me₃P)Ta( ₂-S)₂( ₃-S)Fe(PMe₃)₂]₂ the two [Cl(Me₃P)Ta] units are arranged around one central Fe₂( ₂-S)₂ unit. In [(Me₃P)₄(MeCN)₂Fe^II]²⁺[(Me₃P)₂Ta^IVFe^II ₃( ₃-S)₄Br₄]^2– a [TaFe₃S₄]²⁺ cuboidal arrangement was observed. The complex salt forms a polymeric structure in the solid-state with weak H-bonds between the ions. The [(Me₃P)₂Ta^IVFe^II ₃( ₃-S)₄Br₄]^2– ion was characterised by magnetic measurements showing strong antiferromagnetic interactions between the metal centres.     

Structure and Reactivity of Lithium Enolates. From Pinacolone to Selective C-Alkylations of Peptides. Difficulties and Opportunities Afforded by Complex Structures

The chemistry of lithium enolates is used to demonstrate that complex structures held together by noncovalent bonds (“supramolecules”) may dramatically influence the result of seemingly simple standard reactions of organic synthesis. Detailed structural data have been obtained by crystallographic investigations of numerous Li enolates and analogous derivatives. The most remarkable features of these structures are aggregation to give dimers, tetramers, and higher oligomers, complexation of the metal centers by solvent molecules and chelating ligands, and hydrogen-bond formation of weak acids such as secondary amines with the anionoid part of the enolates. The presence in nonpolar solvents of the same supramolecules has been established by NMR-spectroscopic, by osmometric, and by calorimetric measurements. The structures and the order of magnitude of the interactions have also been reproduced by ab-initio calculations. Most importantly, supramolecules may be product-forming species in synthetic reactions of Li enolates. A knowledge of the complex structures of Li enolates also improves our understanding of their reactivity. Thus, simple procedures have been developed to avoid complications caused by secondary amines, formed concomitantly with Li enolates by the common methods. Mixtures of achiral Li enolates and chiral Li amides can give rise to enantioselective reactions. Solubilization by LiX is observed, especially of multiply lithiated compounds. This effect is exploited for alkylations of N-methylglycine (sarcosine) CH₂ groups in open-chain oligopeptides. Thus, the cyclic undecapeptide cyclosporine, a potent immunosuppressant, is converted into a THF-soluble hexalithio derivative (without epimerization of stereogenic centers) and alkylated by a variety of electrophiles in the presence of either excess lithiumdiisopropyl amide or of up to 30 equivalents of lithium chloride. Depending on the nature of the LiX additive, a new stereogenic center of (R) or (S) configuration is created in the peptide chain by this process. A structure-activity correlation in the series of cyclosporine derivatives thus available is discussed.     

Transition metal nitrosyls as nitrosylation agents : II.Photo-nitrosylation of η5-C5H5V(CO)3L(L = CO,Pz3) by [Co(NO)2Br]2

η⁵-C₅H₅V(NO)₂CO is prepared in 40% yield by the photo-reaction between η⁵-C₅H₅V(CO)₄ and [Co(NO)₂Br]₂.η⁵-C₅H₅V(NO)₂CO reacts by an S_N1 mechanism with various phosphines PZ₃ to yield η⁵-C₅-H₅V(NO)₂PZ₃. The phosphine complexes are also obtained by photo-induced ligand interchange between η⁵-C₅H₅V(CO)₃PZ₃ and [Co(NO)₂Br]₂, or η⁵-C₅H₅V(CO)₄ and Co(NO)₂Br(PZ₃). In all cases, the main cobalt species formed is Co(NO)(CO)₃. While the one-bond vanadiumphosphorus coupling constants of most of the phosphine complexes are virtually the same (ca 410 Hz),the chemical shift values δ(⁵¹V) (?1328 to ?973 ppm rel. VOCl₃) decrease in the order PF₃ > CO > P(OR)₃ > P(alkyl)₃ > PPh₃ > PPh(NEt₂)₂, reflecting the decreasing π-acceptor ability of the ligands. δ(⁵¹V) also decreases in the series of alkylphosphines PR₃ (R = Me, Et, Prⁿ, Buⁱ, Prⁱ, BU^t) as the cone angle of PR₃increases.     

Preparation of polycrystalline Ti-Al-O films by magnetron sputtering ion plating: constitution, structure and morphology

Ti-Al-O layers were deposited on Si-<100> wafers at 500 °C by means of reactive magnetron sputtering ion plating (R-MSIP). An Al-target was sputtered in rf-mode and a Ti-target in dc-mode simultaneously by an oxygen/argon plasma. The influence of the Al- and Ti-sputter powers on composition, structure, and morphology of the Ti-Al-O layers and the binding states of the components were investigated. The analysis with EPMA, XPS, AES and TEM yielded the following results: Ti-Al-O coatings with different Ti, Al, and O contents in the range of TiO₂ to Al₂O₃ were grown. TEM structure analysis revealed: the pure TiO₂ film consisted of the tetragonal phases rutile and anatase; the two structures were found in the titanium-rich Ti-Al-O film, too, but with significant smaller lattice constants. The aluminium-rich Ti-Al-O film displayed the same cubic structure of γ-Al₂O₃ as determined for the pure Al₂O₃ film, but the lattice constant is significant lower. Evaluation of the TEM pattern of the film with a Ti/Al ratio of 0.8 indicates a hexagonal structure with lattice constants similar to those of κ′-Al₂O₃. All films are nanocrystalline and not textured. Received: 24 June 1996 / Revised: 27 December 1996 / Accepted: 4 January 1997