526 research outputs found
Komplexchemie perhalogenierter Cyclopentadiene und Alkine, VII
Coordination Chemistry of Perhalogenated Cyclopentadienes and Alkynes, VII1). - Synthesis of Several Tetrachlorometalloles of Cobalt, Rhodium, and Iridium; Structure of a Iridacyclopentadiene Derivative
The reaction of dichloroethyne with CpCo(PPh3)2, RhCl(EPh3)3 (E = P, As, Sb), and IrCl(N2)(PPh3)2 leads to the formation of complexes containing a tetrachloro-1-metallacyclopentadiene unit. The crystal-structure determination of (Ph3P)2(Cl)- is reported
ZWISCHEN MEISTERWERK UND VIRTUELLER GALERIE: DAS DEUTSCHE MUSEUM AUF DEM WEG INS 21. JAHRHUNDERT
Festvortrag auf dem Akademischen Festakt anlÀsslich des 398. Geburtstages Otto von Guerickes am 23. November 2000 in der Johanniskirche zu Magdeburg
KohlenwasserstoffverbrĂŒckte Komplexe, XXX
Hydrocarbon-Bridged Complexes, XXX. - Nucleophilic Addition of Carbonylmetallates to Cationic Vinyl, Diene, Dienyl and Triene Complexes of Iron, Ruthenium and Cobalt: Di-, Tri-, Tetra- and Pentametallic Complexes with ,- and ,-Hydrocarbon Bridges[Note ][Herrn Professor Ekkehard Lindner zum 60. Geburtstag gewidmet.]
The reactions of [Re(CO)5]-, [Ru(CO)2Cp]-, and [Os(CO)4]2- with [Cp2(OC)2Fe2(-CO)(-1:2-CH=CH2)]+, [Cp*Ru(2:4-1,3,7-octatriene)]+, [(OC)Fe(4-diene)(5-cycloheptadienyl)]+, and [CpCo(5-cyclodienyl)]+ give the nucleophilic adducts whereas with [Mn(CO)5]-, [W(CO)3Cp]-, and [Fe(CO)2Cp]- formation of the corresponding C-C coupling products and of the metal-metal-bonded dimers is observed. The structures of Cp*Ru(-1:2:3-1,5-octadienyl)Re(CO)5 (4), [Cp* Ru(-1:2:3-1,5-octadienyl)]2Os(CO)4 (6), and of (OC)-Fe(4-1,3-cyclohexadiene) (-1:4-1,3-cycloheptadiene)Re(CO)5 (9) have been determined by X-ray diffraction
Synthesis of six-coordinate mono-, bis-, and tris(tetrazolato) complexes via [3 + 2] cycloadditions of nitriles to silicon-bound azido ligands
A convenient synthetic route to poly(tetrazolato) silicon complexes is described based on the four reactive centres of the N-rich, highly endothermic tetraazides of the type Si(N3)4(L2). Hypercoordinate azido(tetrazolato) silicon complexes Si(N3)2(N4C-R)2(L2), R = CH3, C6H5, 4-C6H4CH3 (4a, 5, 6, 7) and Si(N3)2(N4C-L)2 (9, L = 2-C5H4N), L2 = 2,2'-bipyridine, 1,10-phenanthroline, with SiN6 skeletons were synthesised via multiple [3 + 2] dipolar cycloaddition reactions starting from Si(N3)4(L2) and a nitrile. The isolated new complexes were characterised by standard analytical methods, single crystal X-ray diffraction and differential scanning calorimetry (4a,b). Tetrazolato ligand linkage isomerism was observed for complex 4a. The crystallographically characterised methyl tetrazolato complexes and plausible configurational and linkage isomers were evaluated by DFT calculations at the B3LYP/6-311G(d,p) level
Taming Tin(IV) Polyazides
The first charge-neutral Lewis base adducts of tin(IV) tetraazide, [Sn(N3)4(bpy)], [Sn(N3)4(phen)] and [Sn(N3)4(py)2], and the salt bis{bis(triphenylphosphine)iminium} hexa(azido)stannate [(PPN)2Sn(N3)6] (bpy = 2,2âČ-bipyridine; phen = 1,10-phenanthroline; py = pyridine; PPN = N(PPh3)2) have been prepared using covalent or ionic azide-transfer reagents and ligand-exchange reactions. The azides were isolated on the 0.3 to 1â
g scale and characterized by IR and NMR spectroscopies, microanalytical and thermal methods and their molecular structures determined by single-crystal XRD. All complexes have a distorted octahedral Sn[N]6 coordination geometry and possess greater thermal stability than their Si and Ge homologues. The nitrogen content of the adducts of up to 44â% exceed any SnIV compound known hitherto
Homoleptic Low-Valent Polyazides of Group 14 Elements
First examples of coordinatively unsaturated, homoleptic azido complexes of low-valent group 14 elements are reported. A simple strategy uses low-valent precursors, ionic azide transfer reagents and bulky cations to obtain salt-like compounds containing E(N3)3- of Ge(II)/Sn(II) which are fully characterised, including XRD. Remarkably, these compounds are kinetically stable at r.t. and isolable in sub-gram quantities
Metal-induced tautomerization of oxazole and thiazole molecules to heterocyclic carbenes
Protein 3D Structure Computed from Evolutionary Sequence Variation
The evolutionary trajectory of a protein through sequence space is constrained by its function. Collections of sequence homologs record the outcomes of millions of evolutionary experiments in which the protein evolves according to these constraints. Deciphering the evolutionary record held in these sequences and exploiting it for predictive and engineering purposes presents a formidable challenge. The potential benefit of solving this challenge is amplified by the advent of inexpensive high-throughput genomic sequencing
Discrimination based on Gly and Arg/Ser at position 673 between dipeptidyl-peptidase (DPP) 7 and DPP11, widely distributed DPPs in pathogenic and environmental gram-negative bacteria
Porphyromonas gingivalis, an asaccharolytic gram-negative rod-shaped bacterium, expresses the novel Asp/Glu-specific dipeptidyl-peptidase (DPP) 11 (Ohara-Nemoto, Y. et al. (2011) J. Biol. Chem. 286, 38115â38127), which has been categorized as a member of the S46/DPP7 family that is preferential for hydrophobic residues at the P1 position. From that finding, 129 gene products constituting five clusters from the phylum Bacteroidetes have been newly annotated to either DPP7 or DPP11, whereas the remaining 135 members, mainly from the largest phylum Proteobacteria, have yet to be assigned. In this study, the substrate specificities of the five clusters and an unassigned group were determined with recombinant DPPs from typical species, i.e., P. gingivalis, Capnocytophaga gingivalis, Flavobacterium psychrophilum, Bacteroides fragilis, Bacteroides vulgatus, and Shewanella putrefaciens. Consequently, clusters 1, 3, and 5 were found to be DPP7 with rather broad substrate specificity, and clusters 2 and 4 were DPP11. An unassigned S. putrefaciens DPP carrying Ser673 exhibited Asp/Glu-specificity more preferable to Glu, in contrast to the Asp preference of DPP11 with Arg673 from Bacteroidetes species. Mutagenesis experiments revealed that Arg673/Ser673 were indispensable for the Asp/Glu-specificity of DPP11, and that the broad specificity of DPP7 was mediated by Gly673. Taken together with the distribution of the two genes, all 264 members of the S46 family could be attributed to either DPP7 or DPP11 by an amino acid at position 673. A more compelling phylogenic tree based on the conserved C-terminal region suggested two gene duplication events in the phylum Bacteroidetes, one causing the development of DPP7 and DPP11 with altered substrate specificities, and the other producing an additional DPP7 in the genus Bacteroides
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