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51.
Cotton FA Daniels LM Murillo CA Timmons DJ Wilkinson CC 《Journal of the American Chemical Society》2002,124(31):9249-9256
Full characterization of the first homologous series of dimolybdenum paddlewheel compounds having electronic configurations of the types sigma(2)pi(4)delta(x), x = 2, 1, 0, and Mo-Mo bond orders of 4, 3.5, and 3, respectively, has been accomplished with the guanidinate-type ligand hpp (hpp = the anion of 1,3,4,6,7,8-hexahydro-2H-pyrimido[1,2-a]pyrimidine). Essentially quantitative oxidation of Mo(2)(hpp)(4), 1, by CH(2)Cl(2) gives Mo(2)(hpp)(4)Cl, 2. The halide in 2 can be replaced by reaction with TlBF(4) to produce Mo(2)(hpp)(4)(BF(4)), 3. Further oxidation of 2 by AgBF(4) produces Mo(2)(hpp)(4)ClBF(4), 4. The change from bond order 4 (in 1) to 3.5 in Mo(2)(hpp)(4)Cl is accompanied by an increase in the Mo-Mo bond length of 0.061 to 2.1280(4) A. A further increase of 0.044 A in the Mo-Mo distance to 2.172(1) A is observed as the bond order decreases to 3 in 4. At the same time, the Mo-N distances decrease smoothly as the oxidation state of the Mo atoms increases. Electrochemical studies have shown two chemically reversible processes at very negative potentials, E(1)(1/2)= -0.444 V and E(2)(1/2)= -1.271 V versus Ag/AgCl. These correspond to the processes Mo(2)(6+/5+) and Mo(2)(5+/4+), respectively. The latter potential is displaced by over 1.5 V relative to those of the Mo(2)(formamidinate)(4) compounds and the first one has never been observed in such complexes. Thus, in surprising contrast to previously observed behavior of the dimolybdenum unit, when it is surrounded by the very basic guanidinate ligand hpp, there is an extraordinary stabilization of the higher oxidation numbers of the molybdenum atoms. 相似文献
52.
Tetramethyl- and hexamethyl-substituted [2.2]metacyclophane monoenes (10 and 11) are transformed into their corresponding trans-dimethyldihydroethanophenanthrenium dications (14(2+) and 15(2+)) in FSO(3)H x SbF(5) (4:1) and FSO(3)H x SbF(5) (1:1) with SO(2)ClF or SO(2) as the solvent; these 10 pi-dications are equivalent to the C-4/C-5 diprotonated dications of the 2,7-dimethyl derivative of trans-DMDHP, 3a. The trans-12c,12d-dimethyl-12c,12d-dihydrobenzo[e]pyrene (6) reacts with FSO(3)H/SO(2)ClF under surprisingly mild conditions to give initially a persistent diprotonated dication (6H(2)(2+)) and, subsequently, the oxidation dication (6(2+)); the 6(2+):6H(2)(2+) ratio reaches 4:1 after 1 week at low temperature. Protonation of the anti-metacyclophane (13) was also examined. Charge delocalization mode and tropicity in the resulting dications are gauged via detailed NMR studies at 500 MHz. 相似文献
53.
Summary
Determination of Boron in Glass by the Nuclear Track Technique
The nuclear track technique using the10B(n)7Li reaction, has been applied to determine boron in concentration ranges (1.59 to 7.75%) ordinarily considered high for nuclear determinations. Factors limiting the overall precision of the method and restricting the linear dependence of track density on boron concentration are examined. Boron alpha track densities are used to construct planar profiles of boron distribution within the surface region of bulk glass and CVD films. Calibration curves for quantitative lateral profiling of surfaces are constructed and show the selective corrosion of borosilicate glass surface resulting in boron depletion. 相似文献
54.
Abe K Akagi T Anthony PL Antonov R Arnold RG Averett T Band HR Bauer JM Borel H Bosted PE Breton V Button-Shafer J Chen JP Chupp TE Clendenin J Comptour C Coulter KP Court G Crabb D Daoudi M Day D Dietrich FS Dunne J Dutz H Erbacher R Fellbaum J Feltham A Fonvieille H Frlez E Garvey D Gearhart R Gomez J Grenier P Griffioen KA Hoibraten S Hughes EW Hyde-Wright C Johnson JR Kawall D Klein A Kuhn SE Kuriki M Lindgren R Liu TJ Lombard-Nelsen RM Marroncle J Maruyama T Maruyama XK McCarthy J Meyer W 《Physical review letters》1995,74(3):346-350
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The PH bond of dialkylphosphites (dimethylphosphite, 5,5-dimethyl-1,3-dioxa-2-phosphorinane and 4,4,5,5-tetramethyl-1,3-dioxa-2-phospholane) oxidatively adds to irClL2(L = PPh3, AsPh3) and IrCl(PMe2Ph)3 generated in situ to give six-coordinate hydrido(dialkylphosphonato)iridium(III) complexes, e.g. IrHClL2[{(MeO)2-PO}2H] and IrHCl(PMe2Ph)3[PO(OMe)2]. Addition of triphenylphosphine to a solution containing [IrCl(C8H14)2]2 and dimethylphosphite in a 1:2 mol ratio gives a five-coordinate hydrido (dimethylphosphonato)iridium(III) complex IrHCl(PPh3)2{PO(OMe)2}, from which six-coordinate pyridine and acetylacetonato complexes IrHCl(PPh3)2(C5H5N){PO(OMe)2} and IrH(PPh3)2(acac){PO(OMe)2} can be obtained. The ligand arrangements in the various complexes are inferred from IR, 1H and 31P NMR data. 相似文献
59.
J. A. Moore T. D. Mitchell 《Journal of polymer science. Part A, Polymer chemistry》1983,21(5):1305-1314
Polyenaminoesters were prepared by condensation of succinyl succinic ester (SSE) and p-bis-carbomethoxy diacetyl benzene (CDB) with 1,3-bis(3-aminopropyl)-1,1,3,3-tetramethyldisiloxane. Conditions of solvent and temperature were discovered which yielded soluble polymer from SSE after heat treatment. CDB yields only tough, rubbery, insoluble products. 相似文献
60.
A sensitive method for the detection and quantitation of lysergic acid diethylamide (LSD) in urine was developed. After initial solvent extraction, the compound was further purified by liquid-liquid extraction or by solid-phase extraction. The trimethylsilyl derivative of LSD was detected by gas chromatography-mass spectrometry (GC-MS) operated in the electron-impact mode with selected-ion monitoring. The presence of LSD was confirmed by comparing retention times and relative abundances of ions of unknowns with that of a standard. The recovery of this procedure was greater than 89%. The intra-run and inter-run coefficients of variation were less than 5% and less than 7%, respectively. This procedure allows detection of LSD concentrations as low as 29 pg/ml. Quantitation of LSD was linear over the concentration range 50-2000 pg/ml. 相似文献