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.     

Recyclable polyurea-microencapsulated Pd(0) nanoparticles: an efficient catalyst for hydrogenolysis of epoxides

[reaction: see text] Pd nanoparticles (approximately 2 nm in size) microencapsulated in polyurea is an efficient and recyclable catalyst for reductive ring-opening hydrogenolysis of epoxides, using either HCOOH/Et(3)N or H(2) as a hydrogen donor.     

The synthesis and fluxional behavior of the first [2.1.2.1] metacyclophane

8,15,23,30-Tetramethyl[2.1.2.1]metacyclophane,4, is synthesised. Variable temperature ¹Hmr and ¹³Cmr spectra indicate that 4e is the most likely conformation and that at temperatures above 50°C the molecule is fluxional (ΔG^≠₃₂₃ = 15.4 kcal/mole).     

Synthesis and in Vitro Evaluation of N-[[4-[2-(Carboxyl)-1-Cycloalken-1-yl]Phenyl]Methyl]Imidazoles as Nonpeptide Angiotensin II Receptor Antagonists

A series of nonpeptide angiotensin II receptor antagonists was synthesized via palladium-assisted cross coupling of aryl stannane and cycloalkenyl triflates and subsequent alkylation of silyl-protected imidazole. Our compounds, which have a terminal five- to seven-membered cycloalkenyl ring, are compared to DuPont EXP7711, an N-[(2′-carboxybiphenylyl)methyl]imidazole, which has a terminal phenyl moiety. Physicochemical properties of the compounds, such as lipophilicity, steric bulk, conformation, and the relative spatial proximity of the 2-carboxyl and the middle phenyl, are quantitated by computational chemistry. Potency in terms of binding affinity to AT₁ receptors in rat adrenal glomerulosa and rabbit aorta is maximized when the terminal ring is aromatic.