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51.
Gordon K. Anderson Ronald J. Cross Ljubica Manojlovic-Muir Kenneth W. Muir Tihomir Solomun 《Journal of organometallic chemistry》1979,170(3):385-397
The known complex, -(η-C5H5)2Rh2(CO)2(CF3C2CF3) is formed in high yield from (η-C5H5)Rh(CO)2 and CF3FCCF3 at 100°. The less stable -isomer of the complex is obtained in low yield from the same reaction. The infrared, 1H, 19F and 13C NMR spectra of the two isomers are compared. The -isomer undergoes CO scrambling in solution at room temperature, and the variable temperature 13C NMR spectra are consistent with a pairwise bridge opening and closing mechanism. The mechanism is extended to account for the isomerization of to isomer, whihc has a half-life of 12 h at room temperature. The 13C spectrum indicates that the -isomer is static in solution at room temperature. The -isomer is reversibly protonated by protonic acids, and BF4? and PF6? salts of the protonated species can be isolated. The spectroscopic properties of these salts are consistent with protonation at one of the alkynyl-carbons, but it is not possible to distinguish between two alternative structures for the complex cation.Treatment of (η-C5H5)2Rh2(CO)2(CF3C2CF3) with (η-C5H5)Rh(CO)2 gives the trinuclear complex (η-C5H5)3Rh3(CO)(CF3C2CF3) in 80% yield. The analogoug but-2-yne complex is formed from (η-C5H5)3Rh3(CO)3 and MeCCMe. The infrared, 1H, 19F and 13C NMR spectra indicate that the hexafluorobut-2-yne complex exists in two different structural arrangements in solution. One has an edge bridging, and the other a face bridging carbonyl. The proportion of the isomers is affected by the solvent polarity. The spectra of the but-2-yne complex indicate it is fluxional at room temperature, and has a face bridging structure in solution regardless of the polarity of the solvent. Reversible protonation of the hexafluorobut-2-yne complex occurs in protonic acids, and the salt [(η-C5H5)3Rh3(CO)(CF3C2CF3)H]+[BF4]?,H2O can be isolated. The spectroscopic properties of this complex are consistent with a structure incorporating an edge-bridging carbonyl, and probably, an edge-bridging hydride ligand. 相似文献
52.
The magnetic susceptibilities of cobaltocene and chromocene have been measured between 83 and 293 K; for cobaltocene the results suggest an appreciable orthorhombic splitting of the 2∏(σ2πδ4 ground state, whilst for chromocene the data provide further support for the 3Δ(σδ3) ground state previously deduced. 相似文献
53.
Wilkie GD Elliott GI Blagg BS Wolkenberg SE Soenen DR Miller MM Pollack S Boger DL 《Journal of the American Chemical Society》2002,124(38):11292-11294
The scope of intramolecular Diels-Alder and a novel tandem Diels-Alder/1,3-dipolar cycloaddition cascade of 1,3,4-oxadiazoles is disclosed. In the cases examined, the tandem cycloadditions construct three new rings with formation of four new C-C bonds and set all six stereocenters about a central six-membered ring in a single step including three contiguous and four total quaternary centers without a trace of a second diastereomer. 相似文献
54.
55.
Gribble GW Switzer FL Bushweller JH Jewett JG Brown JH Dion JL Bushweller CH Byrn MP Strouse CE 《The Journal of organic chemistry》1996,61(13):4319-4327
The (1)H NMR spectra of 10-benzyl-9,11-diphenyl-10-azatetracyclo[6.3.0.0.(4,11)0.(5,9)]undecane (BnPh(2)()) and 10-methyl-9,11-diphenyl-10-azatetracyclo[6.3.0.0.(4,11)0.(5,9)]undecane (MePh(2)()) decoalesce due to slowing inversion at nitrogen and to slowing isolated bridgehead phenyl rotation. The high nitrogen inversion barriers in MePh(2)() (DeltaG() = 12.2 +/- 0.1 kcal/mol at 250 K) and BnPh(2)() (DeltaG() = 10.6 +/- 0.1 kcal/mol at 215 K) are typical of tertiary amines in which at least one C-N-C bond angle is constrained to a small value. Compared to the minuscule rotation barriers about sp(2)-sp(3) carbon-carbon bonds in simple molecular systems, the bridgehead phenyl rotation barriers in MePh(2)() (DeltaG() = 9.8 +/- 0.1 kcal/mol at 210 K) and BnPh(2)() (DeltaG() = 9.8 +/- 0.1 kcal/mol at 210 K) are unusually high. Molecular mechanics calculations (MMX force field) suggest that the origin of the high phenyl rotation barriers lies in the close passage of an o-phenyl proton and a methyl (or benzylmethylene) proton in the transition state. BnPh(2)() crystallized from hexane as white needles in the monoclinic system Pn. Unit cell dimensions are as follows: a = 12.198(1) ?, b = 6.1399(6) ?, c = 14.938(2) ?, beta = 107.470(4) degrees, V = 1067.1(2) ?(3), Z = 2. In the crystal molecular structure, the imine bridge CNC bond angle in BnPh(2)() is constrained to a small value (96 degrees ). The benzylic phenyl group is oriented gauche to the nitrogen lone pair. 相似文献
56.
57.
Y. A. Gordon V. Jakšić S. Molčanov B. Simon 《Communications in Mathematical Physics》1993,157(1):23-50
We investigate spectral properties of random Schrödinger operators H = - + n()(1 + |n|) acting onl
2(Z
d), where n are independent random variables uniformly distributed on [0, 1].Research partially supported by a Sloan Doctoral Dissertation Fellowship and NSERC under grant OGP-0007901Research partially supported by NSF grant DMS-9101716 相似文献
58.
59.
Rosenstein BS Phelps RG Weinstock MA Bernstein JL Gordon ML Rudikoff D Kantor I Shelton R Lebwohl MG 《Photochemistry and photobiology》1999,70(5):798-806
Sun exposure histories were obtained from a series of patients age 35 or younger following diagnosis and removal of a basal cell carcinoma (BCC). The DNA was extracted from tumor biopsy samples derived from BCC of 10 patients who reported that they did not use sunscreens during youth (age 18 or younger) and 10 patients who routinely employed sunscreens during this age period. Exons 5-9 of the p53 gene were then amplified in three fragments from these samples using a nested polymerase chain reaction (PCR) approach and screened for mutations using an RNA heteroduplex assay. All PCR products displaying evidence of a mutation were sequenced. It was found that 6 of the 10 patients who were not routine sunscreen users displayed mutations in these p53 exons. All of the mutations were located at dipyrimidine sites, five of the six were C-->T transitions and one mutation was a tandem double mutation, consistent with a role for solar UVB in BCC formation. In contrast, only one p53 mutation was detected in the group of 10 patients who routinely employed sunscreens during childhood and adolescence. Hence, a significantly (P = 0.029) lower level of p53 mutations was detected in the BCC obtained from sunscreen users compared with tumors derived from nonusers. These findings suggest that the mechanisms involved in the etiology of skin carcinogenesis differ in sunscreen users compared with people who did not routinely employ sunscreens. These data are also indicative of a protective effect associated with sunscreen use against the formation of p53 mutations. It is possible that the patients who were diagnosed with BCC despite their use of sunscreens possessed a genetic susceptibility for skin cancer formation and developed BCC through a p53-independent pathway. Alternatively, solar UVA wavelengths, that were generally not blocked by the suncare products employed by the sunscreen users, may have played a significant role in BCC development through induction of a mutation(s) in an oncogene and/or a tumor suppressor gene, other than p53, for these patients. 相似文献
60.
Gordon McKay Stephen J. Allen Ian F. McConvey Michael S. Otterburn 《Journal of colloid and interface science》1981,80(2):323-339
A three-step model has been proposed for the adsorption of Astrazone Blue dye (Basic Blue 69) on peat. The initial rate of uptake of dye ions due to physical adsorption and chemisorption (ion exchange) has been correlated using a surface mass transfer coefficient. These coefficients have been determined and expressed in the dimensionless mass transfer form, Sh/Sc0.33, as a function of agitation, initial dye concentration, peat particle size range, dye solution temperature, and mass of peat. 相似文献