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11.
Adler J Becker JJ Blaylock GT Bolton T Brient J Browder T Brown JS Bunnell KO Burchell M Burnett TH Cassell RE Coffman D Cook V Coward DH DeJongh F Dorfan DE Drinkard J Dubois GP Eigen G Einsweiler KF Eisenstein BI Freese T Gatto C Gladding G Grab C Hamilton RP Hauser J Heusch CA Hitlin DG Izen JM Kim PC Köpke L Li A Lockman WS Mallik U Matthews CG Mincer AI Mir R Mockett PM Mozley RF Nemati B Odian A Parrish L Partridge R Pitman D Plaetzer SA Richman JD Sadrozinski HF Scarlatella M Schalk TL 《Physical review letters》1989,62(16):1821-1824
12.
A series of photoreactive complexes of the type Ru(terpy*)(N-N)(L)(2+), where terpy* is 4'-(3,5-ditertiobutylphenyl)-2,2':6',2' '-terpyridine, N-N is the bidentate chelate phen or dmp (phen = 1,10-phenanthroline, dmp = 2,9-dimethyl-1,10-phenanthroline), and L is the monodentate ligand dms, MeBN, or MeOBN (dms = dimethyl sulfide, MeBN = 2,6-dimethyl benzonitrile, MeOBN = 2,6-dimethoxybenzonitrile), has been synthesized and fully characterized by proton NMR spectroscopy, electrospray mass spectrometry, and UV-vis spectroscopy. The X-ray structures of four complexes were also obtained. In neat pyridine, the quantum yields for the photosubsitution of L by pyridine were measured and showed dramatic variations depending on the steric interactions between the spectator bidentate ligand and the leaving monodentate ligand L. The use of dmp instead of phen multiplied the photosubstitution efficiency by a factor of 20-50, depending on L. This effect could be qualitatively correlated to the distortions observed in the X-ray structures of the corresponding complexes. The highly distorted structure of Ru(terpy)(dmp)(dms)(PF(6))(2) showed a very high photosubsitution quantum yield phi = 0.36 in neat pyridine. The high photoreactivity of some of the compounds makes them particularly promising as components of future light-driven molecular machines. 相似文献
13.
P. J. Hauser A. F. Schreiner J. D. Gunter W. J. Mitchell M. K. Dearmond 《Theoretical chemistry accounts》1972,24(1):78-88
MCD, electronic absorption, external heavy atom, and crystal field data are presented for the low energy region (2
E
g, 2
T
1g, 4
T
2g) and high energy region (2
T
2g, 4
T
1g) of Cr(dtp)3, Cr(dtc)3, and Cr(exan)3. At low energy, MCD intensities of 2
E(2
E
g) and 2
E(2
T
g) are as large or larger than 4
T
2g, and the MCD technique is advantageous over electronic absorption in this respect. The MCD positions of 2
E
g and 2
T
1g are nearly the same for these molecules ( 13 kK and 13.6 kK) · 4
T
2g of this region appears trigonally split ( 500 cm–1) in the MCD of dtp but to a smaller extent than in the electronic crystal spectrum of Lebedda and Palmer ( 600 cm–1). MCD did not resolve such components for exan and dtc. The higher energy region includes 2
T
2g and 4
T
1g, and the combined MCD and electronic absorption data of the three compounds taken together lead us to conclude the ordering 2
A
1(2
T
2g)<2
E(2
T
2g)<4
E(4
T
1g). The potentially useful external heavy atom affect on the solution-observed electronic 2
E and 4
E bands of Cr(dtp)3 did not shed additional light on this order of E states. Finally, it is concluded that the order of 4
T
1g and 2
T
2g cannot be decided from O
h crystal field calculations because of experimental uncertainties about choosing centers of gravity. In addition, 4
T
1g and 2
T
2g are close together so that ordering 2
E<4
E does not guarantee 2
T
2g<4
T
1g. However, it can be concluded that the ratio C/B4 is not correct, whereas the larger 7<(C/B)<8 is consistent with the data of all three molecules because of small B parameters ( 0.4). Locating OO transitions may somewhat decrease C/B and Dq.
Presented in part at the 161st American Chemical Society National Meeting, Los Angeles, California, March–April, 1971.
NDEA Pre-Doctoral Fellow. 相似文献
Zusammenfassung In der vorliegenden Arbeit werden folgende Meßergebnisse mitgeteilt; MCD, elektronische Absorption, Einfluß eines äußeren schweren Atoms sowie Kristallfelddaten für den Bereich niedriger Energie (2 E g, 2 T 1g, 4 T 2g) und den Bereich hoher Energie (2 T 2g, 4 T 1g) von Cr(dtp)3, Cr(dtc)3 und Cr(exan). Bei niedriger Energie sind die MCD-Intensitäten von 2 E(2 E g) und 2 E(2 T 1g) genau so groß, oder größer als 4 T 2g, und die MCD-Technik bietet Vorteile gegenüber der elektronischen Absorptionsmethode. Die MCD-Werte von 2 E g und 2 T 1g sind für die genannten Moleküle etwa gleich ( 13 kK und 13,6 kK). 4 T 2g dieses Gebietes erscheint trigonal aufgespalten ( 500 cm–1) bei MCD von dtp, aber in einem geringeren Maß als im elektronischen Kristallspektrum von Lebedda und Palmer ( 600 cm–1) MCD löste solche Komponenten bei exan und dtc nicht auf. Der Bereich höherer Energie enthält 2 T 2g und 4 T 1g, und aus der Kombination von Daten der MCD-Methode sowie der elektronischen Absorption schlossen wir auf die Anordnung 2 A 1g(2 T 2g)<2 E(2 T 2g)<4 E(4 T 1g). Der möglicherweise nützliche Effekt eines äußeren schweren Atoms auf die in Lösung beobachteten elektronischen 2 E- und 4E-Banden von Cr(dtp)3 brachte bezüglich dieser Anordnung der E-Zustände nichts Neues. Weiterhin wird gefolgert, daß die Ordnung von 4 T 1g und 2 T 2g nicht aus O h-Kristallfeldberechnungen entschieden werden kann, da experimentelle Unsicherheiten bezüglich der Wahl von Schwerpunkten bestehen. Außerdem liegen 4 T 1g und 2 T 2g nahe zusammen, sodaß aus der Anordnung 2 E<4 E nicht notwendig 2 T 2g<4 T 1g folgt. Es kann jedoch gefolgert werden, daß das Verhältnis C/B4 nicht korrekt ist, während 7<(C/B)<8 konsistent mit den Daten aller drei Moleküle ist, da die B-parameter klein sind (0,4). Die Vokalisierung der OO-Übergänge könnten C/B und Dq etwas erniedrigen.
Presented in part at the 161st American Chemical Society National Meeting, Los Angeles, California, March–April, 1971.
NDEA Pre-Doctoral Fellow. 相似文献
14.
Gallo E Caselli A Ragaini F Fantauzzi S Masciocchi N Sironi A Cenini S 《Inorganic chemistry》2005,44(6):2039-2049
A reproducible synthesis of a competent epoxidation catalyst, [Ru(VI)(TPP)(O)2)] (TPP = tetraphenylporphyrin dianion), starting from [Ru(II)(TPP)(CO)L] (L = none or CH3OH), is described. The molecular structure of the complex was determined by using ab initio X-ray powder diffraction (XRPD) methods, and its solution behavior was in detail investigated by NMR techniques such as PGSE (pulsed field gradient spin-echo) measurements. [Ru(IV)(TPP)(OH)]2O, a reported byproduct in the synthesis of [Ru(VI)(TPP)(O)2], was synthesized in a pure form by oxidation of [Ru(II)(TPP)(CO)L] or by a coproportionation reaction of [Ru(VI)(TPP)(O)2] and [Ru(II)(TPP)(CO)L], and its molecular structure was then determined by XRPD analysis. [Ru(VI)(TPP)(O)2] can be reduced by dimethyl sulfoxide or by carbon monoxide to yield [Ru(II)(TPP)(S-DMSO)2] or [Ru(II)(TPP)(CO)(H2O)], respectively. These two species were characterized by conventional single-crystal X-ray diffraction analysis. 相似文献
15.
Charlotte Froese Fischer 《International journal of quantum chemistry》1975,9(2):273-285
Results are reported for multiconfiguration Hartree–Fock studies of correlation in the lithium ground state, which maintain orthogonality of orbitals within a configuration. It is shown that when the 1s- and 2s-orbitals are fixed at their Hartree–Fock value, configurations for which Brillouin's theorem holds may be important, particularly for atomic properties other than energy. The Fermi contact term is considered as an example. 相似文献
16.
The oxidative decomposition of various ketones (including acetone, 2-butanone, 4-heptanone, cyclopentanone and cyclohexanone) over dehydrated TiO(2) (P25) powder is investigated by electron paramagnetic resonance (EPR) spectroscopy. For the first time, a series of thermally unstable radical intermediates are observed both on the activated and reduced TiO(2) surface, depending on the adopted experimental conditions. These radical intermediates are identified as organoperoxy-based species of general formula ROO(.-) and RCO(3) (.-). They are formed by reaction of photogenerated charge carriers (either trapped electrons or trapped holes) with the adsorbed ketones in the presence of molecular oxygen. The organoperoxy intermediates are thermally unstable and decompose at temperatures in the region of 180-250 K. This work demonstrates that free-radical pathways involving both organoperoxy and superoxide radicals can be responsible for the thermal- and photodecomposition of ketones over polycrystalline TiO(2) (P25). 相似文献
17.
Trifluoromethanesulfonic (triflic) acid is an excellent catalyst for inducing overall 5-endo cyclisation of homoallylic sulfonamides [e.g. 4] to give pyrrolidines [e.g. 5]. In competitive experiments, pyrrolidines or homopiperidines are formed in preference to piperidines, even when the latter would be obtained by trapping a tertiary carbocation. Cationic cascades terminated by a sulfonamide group are viable for the efficient formation of polycyclic systems. 相似文献
18.
The efficient catalytic activation of donor–acceptor aminocyclopropanes lacking the commonly used diester acceptor is reported here in a (3 + 2) dearomative annulation with indoles. Bench-stable tosyl-protected aminocyclopropyl esters were converted into cycloadducts in 46–95% yields and up to 95 : 5 diastereomeric ratio using catalytic amounts of triethylsilyl triflimide. Tricyclic indoline frameworks containing four stereogenic centers including all-carbon quaternary centers were obtained.A catalytic dearomatization of indoles with D–A aminocyclopropane monoesters for the synthesis of highly substituted indolines. 相似文献
19.
Metz AW Ireland JR Zheng JG Lobo RP Yang Y Ni J Stern CL Dravid VP Bontemps N Kannewurf CR Poeppelmeier KR Marks TJ 《Journal of the American Chemical Society》2004,126(27):8477-8492
A series of low-melting, thermally stable cadmium metal-organic chemical vapor deposition (MOCVD) precursors have been synthesized, structurally and spectroscopically characterized, and implemented in growth of highly conductive and transparent CdO thin films. One member of the series, bis(1,1,1,5,5,5-hexafluoro-2,4-pentanedionato)(N,N-diethyl-N',N'-dimethyl-ethylenediamine)cadmium(II), Cd(hfa)(2)()(N,N-DE-N',N'-DMEDA), represents a particularly significant improvement over previously available Cd precursors, owing to the low melting point and robust thermal stability. High-quality CdO films were grown by MOCVD on glass and single-crystal MgO(100) between 300 and 412 degrees C. Film growth parameters and substrate surface have large effects on microstructure and electron carrier transport properties. Enhanced mobilities observed for highly biaxially textured films grown on MgO(100) vs glass are attributed, on the basis of DC charge transport and microstructure analysis, to a reduction in neutral impurity scattering and/or to a more densely packed grain microstructure. Although single-grained films grown on MgO(100) exhibit greater mobilities than analogues with discrete approximately 100 nm grains and similar texture, this effect is attributed, on the basis of charge transport and Hall effect measurements as well as optical reflectivity analysis, to differences in carrier concentration rather than to reduced grain boundary scattering. Unprecedented conductivities and mobilities as high as 11,000 S/cm and 307 cm(2)/V.s, respectively, are obtained for epitaxial single-grained films (X-ray diffraction parameters: fwhm(omega) = 0.30 degrees, fwhm(phi) = 0.27 degrees ) grown in situ on MgO(100) at a relatively low temperature (400 degrees C). 相似文献
20.
The enantiomers of adrenaline, noradrenaline, ephedrine and pseudoephedrine were separated by capillary electrophoresis on a micromachined device. Detection was carried out with a new two-electrode amperometric detector, eliminating the need for individual counter and reference electrodes. Separation of the isomers was achieved by employing carboxymethyl-beta-cyclodextrin as chiral selector in the buffer, partly with the additional inclusion of the crown ether 18-crown-6. Plate numbers of up to 20,000, chiral resolutions of 2.5 and detection limits of the order of 10(-7) M were achieved. All separations were completed in less then 3 min. 相似文献