Umsetzungen von Ferrocenol und 1,1′-Ferrocendiol mit Cyclotriphosphazenen,P3N3F6 und P3N3Cl6

Reactions of Ferrocenol and 1,1′-Ferrocendiol with Cyclotriphosphazenes, P₃N₃F₆ and P₃N₃Cl₆ The hexahalogeno-cyclotriphosphazenes, P₃N₃X₆ (X ? F ( 1 a ), Cl ( 1 b )), react with ferrocenol (FcOH) in a molar ratio 1 : 1 to give the ferrocenoxy derivatives, FcO[P₃N₃X₅] (X ? F ( 3 a ), Cl ( 3 b )); in an analogous manner the tetrameric ring P₄N₄Cl₈ ( 2 b ) is converted to FcO[P₄N₄Cl₇] ( 4 b ).

1 Abkürzungen: Fc = Ferrocenyl, (C₅H₅)Fe(C₅H_4?); fc = 1,1′-ferrocendiyl, Fe(C₅H_4?)₂; rc = 1,1′-ruthenocendiyl, Ru(C₅H_4?)₂. Fluorphosphazene werden mit a , Chlorphosphazene mit b gekennzeichnet.

With 1,1′-ferrocenediol, (fc(OH) ₂ ), the cyclo triphosphazenes react in a molar ratio 1 : 1 to produce fcO ₂ [P ₃ N ₃ X ₄ ] (X ? F ( 5 a ), Cl ( 5 b )). According to the x-ray structure analysis, the 1,1′-ferrocenediolato group in 5 a , b is bound to two different phosphorus atoms. On the contrary, the 1,1′-ferrocenedithiolato- and 1,1′-ferrocenediselenolato units in fcS ₂ [P ₃ N ₃ X ₅ ] (X ? F ( 6 a ), Cl ( 6 b )) and fcSe ₂ [P ₃ N ₃ X ₅ ] (X ? F ( 7 a ), Cl ( 7 b )) are attached to only one phosphorus atom, and spirocyclic 1,3-dichalcogena-2-phospha-[3]ferrocenophanes are formed. All new products have been characterized on the basis of their ¹ H, ¹³ C and ³¹ P NMR as well as EI mass spectra. The molecular structures of 5 a , b and 6 a have been determined by x-ray structure analyses.     

Synthesis of s-triazolocycloalkyl-, s-triazolobenzocycloalkyl-, and s-triazolocycloalkylhydrothiadiazines

The reaction of cyclic-α-haloketones with 5-subslituted-4-amino-4H-1,2,4-triazole-3-lhiols gave s-triãzolocycloalkylhydrothiadiazines and s-triazolobenzocycloalkylthiadiazines. Reduetion of the 5,5a-imine bond of the s-triazoloeycloalkylthiadiazines gave s-triazolocycloalkylhydrothia-diazines.     

Hierarchical assembly of helicate-type dinuclear titanium(IV) complexes

The ligands 4-7-H(2) were used in coordination studies with titanium(IV) and gallium(III) ions to obtain dimeric complexes Li(4)[(4-7)(6)Ti(2)] and Li(6)[(4/5a)(6)Ga(2)]. The X-ray crystal structures of Li(4)[(4)(6)Ti(2)], Li(4)[(5b)(6)Ti(2)], and Li(4)[(7a)(6)Ti(2)] could be obtained. While these complexes are triply lithium-bridged dimers in the solid state, a monomer/dimer equilibrium is observed in solution by NMR spectroscopy and ESI FT-ICR MS. The stability of the dimer is enhanced by high negative charges (Ti(IV) versus Ga(III)) of the monomers, when the carbonyl units are good donors (aldehydes versus ketones and esters), when the solvent does not efficiently solvate the bridging lithium ions (DMSO versus acetone), and when sterical hindrance is minimized (methyl versus primary and secondary carbon substituents). The dimer is thermodynamically favored by enthalpy as well as entropy. ESI FT-ICR mass spectrometry provides detailed insight into the mechanisms with which monomeric triscatecholate complexes as well as single catechol ligands exchange in the dimers. Tandem mass spectrometric experiments in the gas phase show the dimers to decompose either in a symmetric (Ti) or in an unsymmetric (Ga) fashion when collisionally activated. The differences between the Ti and Ga complexes can be attributed to different electronic properties and a charge-controlled reactivity of the ions in the gas phase. The complexes represent an excellent example for hierarchical self-assembly, in which two different noncovalent interactions of well balanced strengths bring together eleven individual components into one well-defined aggregate.     

Synthesen von Carotinen mit ψ-Endgruppen und (Z)-Konfiguration an terminalen konjugierten Doppelbindungen

Syntheses of Carotenes with ψ-End Groups and (Z)-Configuration at Terminal Conjugated Double Bonds Five carotenes bearing (5Z)-ψ-end groups were synthesized and carefully characterized: (5Z)-lycopene ( 6 ), (5Z5′Z)-lycopene ( 7 ), (5′Z)-neurosporene ( 8 ), (5′Z)-β,ψ-carotene ( 12 ), and (5′Z)-ε,ψ-carotene ( 14 ).     

Upper limit for thermal direct photon production in heavy-ion collisions at 60 and 200A·GeV

The production of direct photons has been investigated in reactions ofp and¹⁶O projectiles at 60 and 200A·GeV with C and Au nuclei. Photon and ⁰ spectra have been measured in the pseudorapidity range 1.52.1 for the transverse momentum region 0.4 GeV/cp _T 2.8 GeV/c employing the lead-glass spectrometer SAPHIR. An upper limit of 15% at the 90% confidence level for the direct photon signal relative to the neutral pion production is obtained from the comparison of measured photon spectra with Monte Carlo simulations of the hadronic background based on the reconstructed yield of ⁰ and mesons. Consequences for a possible phase transition to a quark-gluon plasma are discussed.     

Dimetallic Complexes with Bridging Seven-membered Cycloolefins. Synthesis,Multinuclear NMR.-Spectroscopic Properties and Structure

The synthesis of dimetallic olefin complexes of the type L¹M¹C₇H₇M²L² (M¹ = Fe, Co, Rh; M² = Rh, Ir, Pd; L¹ = CO, C₅H₅; L² = diene, allyl, P(OR)₃) is described. The fluxional structures were investigated by ¹³C-, ⁵⁷Fe- and ¹⁰³Rh-NMR.-spectroscopy, and a cisoid dimetallic coordination, including a (metal, metal)-bond, can be deduced for the C₇H₇-ring. ⁵⁷Fe- and ¹⁰³Rh-chemical shifts give indications for the charge distribution in the 34e-complexes. The homodimetallic complex (Cp)Rh(tropone)Rh(Cp) ( 13 , Cp = cyclopentadienyl) and the corresponding 2-methoxytropone complex 14 were synthesized in addition to the above mentioned complexes. A fluxional bis(1-3-η-allyl)-coordination of the two Rh-atoms was derived from the temperature-dependent ¹³C-NMR.-spectra. A spin simulation of the (Cp)-multiplets of 12 and 13 yields information about (Rh, Rh)-spin-coupling which amounts to ≈5 Hz at 30°.