Air-stable liquid clathrates. 1. Crystal structure of [NBu4][Br3] and reactivity of the [NBu4][Br3]·5 C6H6 liquid clathrate

[NBu₄][Br₃] interacts with C₆H₆ to form an air-stable liquid clathrate. The tribromide anion reacts with phenol to give para-bromophenol in>95% yield. The HBr which is generated in the reaction combines with the Br^– anion to form [Br-H-Br]^–. The latter forms the basis for a new liquid clathrate, [NBu₄][Br-H-Br]·n C₆H₆. The parent salt, [NBu₄][Br₃], crystallizes in the monoclinic space group C2/c witha=12.983(5),b=10.380(7),c=16.222(6) Å,=93.93(3)°, andD _c =1.47 g cm^–3 forZ=4. The final R value is 0.068 based on 787 observed reflections.     

Variable flip angle imaging and fat suppression in combined gradient and spin-echo (GREASE) techniques

Conventional "proton density" and "T2-weighted" spin-echo images are susceptible to motion induced artifact, which is exacerbated by lipid signals. Gradient moment nulling can reduce motion artifact but lengthens the minimum TE, degrading the "proton density" contrast. We designed a pulse sequence capable of optimizing proton density and T2-weighted contrast while suppressing lipid signals and motion induced artifacts. Proton density weighting was obtained by rapid readout gradient reversal immediately after the excitation RF pulse, within a conventional spin-echo sequence. By analyzing the behavior of the macroscopic magnetization and optimizing excitation flip angle, we suppressed T1 contribution to the image, thereby enhancing proton density and T2-weighted contrast with a two- to four-fold reduction of repetition time. This permitted an increased number of averages to be used, reducing motion induced artifacts. Fat suppression in the presence of motion was investigated in two groups of 8 volunteers each by (i) modified Dixon technique, (ii) selective excitation, and (iii) hybrid of both. Elimination of fat signal by the first technique was relatively uniform across the field of view, but it did not fully suppress the ghosts originating from fat motion. Selective excitation, while sensitive to the main field inhomogeneity, largely eliminated the ghosts (0.21 +/- 0.05 vs. 0.29 +/- 0.06, p less than 0.01). The hybrid of both techniques combined with bandwidth optimization, however, showed the best results (0.17 +/- 0.04, p less than 0.001). Variable flip-angle imaging allows optimization of image contrast which, along with averaging and effective fat suppression, significantly improves gradient- and spin-echo imaging, particularly in the presence of motion.     

Multinuclear magnetic resonance studies on intramolecular chalcogen-tin coordination in compounds of the type Me2Sn(X)CH2CH2P(E)Ph2 (X = Halogen, E = Chalcogen)

Multinuclear magnetic resonance data for the title compounds are presented and discussed. The intramolecular coordination observed in the solid state is shown to be retained in solution. The best probes for the presence or absence of pentacoordination at tin are provided by the various tin-element coupling constants, although chemical shifts are in some cases also informative. A selenium-proton correlated spectrum indicated that the coupling constant ¹J(Sn,Se) has a positive sign.     

The renaissance of palladium(II)-catalyzed oxidation chemistry

Palladium(II)-catalyzed oxidations constitute a paramount reaction class but have remained immature over the past few decades. Recently, this field has reappeared at the forefront of organometallic catalysis. This emerging area article outlines recent developments in palladium(II)-catalyzed oxidation chemistry with discussion of potential future growth.     

Electronic structures and MCD spectra of trigonal Cr(III)S6 systems

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.

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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.

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Presented in part at the 161st American Chemical Society National Meeting, Los Angeles, California, March–April, 1971.

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NDEA Pre-Doctoral Fellow.     

Curium isotopes in Chernobyl fallout

In nuclear reactors plutonium and transplutonium isotopes are produced by multiple neutron capture of uranium and plutonium and are important for the energy production and their composition reflects the core burnout. Under normal operation these elements are not released to the environment in significant amounts. There are accordingly very few areas or source terms where exotic transplutonium elements, such as curium isotopes, can be studied in the environment. The Chernobyl accident provided a complex spectrum of fission and activation products in fallout while the relative amounts, compared to the core inventory, of refractory elements such as transuranium and transplutonium elements were small. The major alpha-activity consisted of ²⁴²Cm (T _1/2 = 163 d) that would have decayed after a few years. In this study we have demonstrated the presence of so called supported ²⁴²Cm from the long-lived ²⁴²Am^m (T _1/2 = 141 a) in environmental samples, following fallout from the Chernobyl accident. It has also been possible to assess the core burn up by using the data obtained for the Cm isotopes. The curium isotopes ²⁴³Cm (T _1/2 = 29.1 a) and ²⁴⁴Cm (T _1/2 = 18.1 a) cannot be resolved by conventional alpha-spectrometry. The assessment of these isotopes in environmental samples contaminated from the Chernobyl accident has been made by studying the effective half-life of the mixture of the isotopes. The data are compared with those previously obtained by high-resolution alpha-spectrometry and spectral deconvolution.