The present structure determination of di‐μ‐hydroxo‐bis{[N,N′‐bis(dipiperidinomethylene)propane‐1,3‐diamine‐κ2N,N′]copper(II)} bis(hexafluorophosphate), [Cu2(OH)2(C25H46N6)2](PF6)2, is the first to crystallographically characterize a Cu2(μ‐OH)2 complex with a bidentate guanidine ligand. The cation lies on a crystallographic inversion centre and shows planar fourfold coordination of the copper centres. The Cu2(μ‐OH)2 species can be distinguished from Cu2(μ‐O)2 by the Cu—O bond lengths. The packing is determined by strong intermolecular anion–cation hydrogen bonds. 相似文献
In the course of investigations on optical properties resulting from the interaction of fluorides with alumosilicate host materials and rare earth guests, a well defined BF4– ion wasfound to be incorporated within the sodalite of composition Na8Al6Si6O24(BF4)2. The resulting cubic molecular structure, which was determined by Rietveld methods (space group P4 n, a = 906.91 pm, wRp = 0.045, Rp = 0.027), contains one anion in each sodalite cage and is, contrarily to expectations, thermally stable. NMR spectroscopic investigations indicated a fast rotatory motion of the BF4– tetrahedra at room temperature and agreed with the tetrahedral BF4– ions found in IR and Raman spectra. Preliminary attempts to obtain a luminescent material by incorporation of Eu3+ through aqueous ion exchange only yielded low rare earth concentrations, giving rise to characteristic red emission lines at 581 nm (5D0 → 7F1) and 615 nm (5D0 → 7F2) in a 1:2 intensity ratio. The material unexpectedly exhibited a strong broad band emission at 520 nm after calcination under Ar, which is attributed to the formation of an Eu2+ species. Further calcination under air partially reestablished the Eu3+ emission. 相似文献
The reaction of 2,2′‐Bis(2N‐(1,1′,3,3′‐tetramethyl‐guanidino))diphenylene‐amine (TMG2PA) ( 1 ) with CuI in MeCN results in the formation of [CuII(TMG2PAamid)I] ( 2 ) indicatingthat CuI is the target of an oxidative attack of the N‐H proton of the ligand which itself is converted to molecular hydrogen. In contrast, if [Cu(MeCN)4][PF6] is used as the CuI source, [CuI2(TMGbenz)2][PF6]2 ( 3 ) is obtained instead. The use of the non‐coordinating counterion [PF6]– apparently prevents CuI from oxidation but induces itself a cyclisation reaction within the ligand which results in the formation of a benzimidazole‐guanidine ligand. 相似文献
The reaction of cis-[RuCl2(P–P)(N–N)] type complexes (P–P = 1,4-bis(diphenylphosphino)butane or (1,1′-diphenylphosphino)ferrocene; N–N = 2,2′-bipyridine or 1,10-phenantroline) with monodentate ligands (L), such as 4-methylpyridine, 4-phenylpyridine and benzonitrile forms [RuCl(L)(P–P)(N–N)]+ species. Upon characterization of the isolated compounds by elemental analysis, 31P{1H} NMR and X-ray crystallography it was found out that the type of the L ligand determines its position in relation to the phosphorus atom. While pyridine derivatives like 4-methylpyridine and 4-phenylpyridine coordinate trans to the phosphorus atom, the benzonitrile ligand (bzCN), a good π acceptor, coordinates trans to the nitrogen atom. A 31P{1H} NMR experiment following the reaction of the precursor cis-[RuCl2(dppb)(phen)] with the benzonitrile ligand shows that the final position of the entering ligand in the complex is better defined as a consequence of the competitive effect between the phosphorus atom and the cyano-group from the benzonitrile moiety and not by the trans effect. In this case, the benzonitrile group is stabilized trans to one of the nitrogen atoms of the N–N ligand. A differential pulse voltammetry experiment confirms this statement. In both experiments the [RuCl(bzCN)(dppb)(phen)]PF6 species with the bzCN ligand positioned trans to a phosphorus atom of the dppb ligand was detected as an intermediate complex. 相似文献
New class of air‐stable catalysts for lactide polymerisation: Guanidine–pyridine hybrid ligands (picture, left) were used to prepare a series of zinc complexes (e.g., depicted cation [ZnL2(CF3SO3)]+, where L is the quinoline‐containing ligand with R1=R2=R3=R4=Me), in which the ligand binds through two different N‐donor atoms. The zinc complexes show high activity in ring‐opening polymerisation of d,l ‐lactide (right), giving polylactide with molecular masses up to 176 000 g mol?1 and in high yield.
Cage chirality : Cyclic addition reactions of chirally modified stannyl‐1,2,4‐triphospholes with tBuC?P leads to stannylated P5‐deltacyclenes in high yields as separable 1:1 mixtures of diastereomers. Destannylation of a separated diastereomer gives a single enantiomer of an optically pure P? C cage compound. The novel cage‐chiral P5C4 unit (shown here) dominates the chiroptical properties, not only of the isolated enantiomer, but of the diastereomeric compounds as well.
Although free from structural disorder , the new intermetallic compound Cd13?xInySb10 (see figure) displays similarly low thermal conductivity values as disordered thermoelectric β‐Zn4Sb3 with an isostructural framework.
To address people's concerns of exogenous oxytocin (OT) administration to lactating bovines, a study was undertaken to (a) establish an enzyme immunoassay (EIA) for OT determination in milk, (b) quantify OT in milk of cows administered OT, and (c) study influence of pasteurization on OT stability in milk. A sensitive EIA validated according to the criteria of European Union—Decision 2002/657/EC was developed for OT in skim milk in an analytical range of 10-250 pg mL−1 with a decision limit (CCα) of 30 pg mL−1 and detection capability (CCβ) of 41.5 pg mL−1. Milk samples collected from cows (n = 38) administered either 25 or 50 IU OT prior to milking were investigated for the presence of OT. There was no significant difference among both groups with the mean concentrations of OT being 15.8 and 14.9 pg mL−1 for cows subjected to 25 and 50 IU OT administration, respectively. The OT levels in skim milk of control cows (n = 30; untreated) were basal (around 10 pg mL−1). All the analyzed milk samples were below the CCα value of 30 pg mL−1. Pasteurization of OT spiked milk samples at different temperature and sample holding conditions reduced the immunological activity of OT to 43% at 110 °C. However, no further decline occurred in the immunological activity with increased pasteurization temperature and time. It was concluded that the milk OT concentrations after OT administrations were minimal and below the assay decision limit. However, OT was quite stable to pasteurization in OT spiked milk. 相似文献