Chain “stationary” insertion mechanism and production of isotactic polypropylene with C 1 symmetric catalyst systems

In this contribution, the stereochemistry of propylene insertion/propagation reactions with a variety of C ₁ symmetric metallocene catalysts, containing bridged cyclopentadienyl-fluorenyl ligand for the preparation of highly stereoregular polypropylene is presented. The impact of the distal substitutent’s size and composition and changes that the catalytic sites undergo upon such substitution is elaborated. A comprehensive mechanism is proposed to explain the resulting catalytic changes that bring about the irreversible C _s/C ₁ site transformation and tactic behavior inversion. Furthermore the cyclopentadienyl’s combined distal/proximal and fluorenyl’s frontal substituent effects on molecular weight, regio-, and stereoregularity of the final polymers are discussed. Finally, stereoselectivities of C ₂ and C ₁ symmetric catalyst systems are compared. It is shown that current high performance C ₁ symmetric catalyst systems with central site chirality can be isotactic selective as well or even better in certain aspects than the C ₂ symmetric bridged bisindenyl-based metallocene catalysts. The text was submitted by the authors in English.     

Die Kristall- und MolekülStruktur von N,N′-Bis-(trimethylsilyl)-oximidsäure-bis(trimethylsilyl)-ester

The Crystal and Molecular Structure of N,N′-Bis(trimethylsilyl) Oximidic Acid Bis (trimethylsilyl) Ester The X-ray structure analysis of the reaction product of oxalyl chloride with sodium bis(trimethylsilyl) amide formulated by PUMP and ROCHOW as N,N′-bis(trimethylsilyl) oximidic Acid bis (trimethylsilyl) ester shows that the suggested structure is correct for the solid state. The compound crystallizes in the space group P1 with a = 9.948(4), b = 6.612(3), c = 10.370(4) Å, α = 88.87(6), β = 116.95(4), γ = 98.23(6)°, and Z = 1. The molecule manifests symmetry 1 .     

EXCITATION ENERGY TRANSFER IN THE CRYPTOPHYTES. FLUORESCENCE EXCITATION SPECTRA AND PICOSECOND TIME-RESOLVED EMISSION SPECTRA OF INTACT ALGAE AT 77 K

Excitation spectra of chlorophyll- a (Chl- a ) fluorescence in intact cells of Cryptomonas ovata, Chroomonas pauciplastida and Chroomonas salina were determined at 77 K. For all species the excitation spectra for emission from Chl- a associated with photosystem II (PSII) showed increased contributions by a carotenoid (493 nm) and phycobiliproteins, and decreased contributions by carotenoid (417 nm, 505 nm) and Chl- a (445 nm) as compared to excitation spectra for emission from Chl- a associated with photosystem I (PSI). Excitation spectra of C. salina and C. ovata showed an increased contribution by Chl- c ² to PSII Chl- a fluorescence emission. In all three species the absorbance band positions of Chl- a , as determined from the excitation spectra, were similar to those previously described in green plants. green algae and phycobilisome-containing organisms. Time-resolved 77 K fluorescence emission spectra of C. ovata and C. salina showed successive emission from both phycoerythrin and Chl- c ², PSII Chl- a , and PSI Chl- a. C. pauciplastida showed successive emission from phycocyanin, PSII Chl- a , and PSI Chl- a. Spectral red-shifts with time were observed for the phycobiliprotein peaks in all three species. The fluorescence decay of phycoerythrin in C. ovata and C. salina was faster than that of phycocyanin in C. pauciplastida. The results are discussed in relation to the organization of the antenna pigments of PSII and PSI in the cryptophyte algae.     

Isolierung und struktur des dreikernigen hexamethylbenzolzirkonium-komplexes [(Me6C6)3Zr3Cl6]2+ [(Al2Cl7)−]2

Crystals of the trinuclear complex [(Me₆C₆)₃Zr₃Cl₆][Al₂Cl₇]₂ have been obtained from the reaction of ZrCl₄, hexamethylbenzene, AlCl₃, and Al in benzene. They are monoclinic, space group C2/2, with Z  4 and lattice parameters a 14.167(3), b 27.779(7), c 15.721(3) Å and β 94.27(4)°. The Zr atoms form a regular triangle. Each pair of Zr atoms is bridged by two Cl atoms. The fifth coordination site of each Zr atom is occupied by a h⁶-Me₆C₆ group. The cation is almost isostructural with the known trinuclear cation [(Me₆C₆)₃Nb₃Cl₆]²⁺. Important distances are: ZrZr 3.35, ZrCl 2.56, and Zrcenter of C₆ ring 2.17 Å. One of the two independent [Al₂Cl₇]^? anions occurs in a staggered conformation and one occurs in an eclipsed conformation.     

Darstellung,struktur und eigenschaften des dreikernigen titankomplexes (π-C2H5)2TiClOTi(π-C5H5)ClOTiCl(π-C5H5)2·CHCl3

The trinuclear titanium(IV) complex (π-C₅H₅)₂TiClOTi(π-C₅H₅)ClOTiCl(π-C₅H₅)₂ · CHCl₃ is formed by hydrolysis of (π-C₅H₅)₂TiCl₂ at pH > 3.5 and can be isolated in the crystalline state from the reaction of (π-C₅H₅)₂TiCl₂ with Ag₂O and water in chloroform. Its structure is determined by X-ray analysis.