Determination of plutonium by secondary coulometric titration with internally generated iron(II)

The method for plutonium determination based on secondary controlled-potential coulometry, as described by SHULTS, is applied for analysis in the range of 0.1–5 mg plutonium. The method involves the oxidation of plutonium to Pu(VI) with perchloric acid followed by its reduction by an internally generated ferrous mediator. This is a two step procedure, involving the reduction of Pu(VI) and Fe(III) to a mixture of Pu(III) and Fe(II), followed by the oxidation of Pu(III) and Fe(II) to Pu(IV) and Fe(III), respectively. The net results is the reduction of Pu(VI) to Pu(IV), measured as the difference between the currents consumed during the reduction and oxidation steps. The original method of SHULTS involves 10–25 mg plutonium for each determination. Since the present method is intended for the analysis of smaller amounts of plutonium, the oxidation procedure described in the original version had to be modified. The method is found to work satisfactorily with a precision better than 0.1% at 5 mg level and 1.2% for 0.1 mg plutonium.     

Reductive Catenation of Phosphine Antimony Complexes

Reactions of triarylphosphines with fluoroantimony(III) triflates give phosphine antimony(III) complexes, which undergo spontaneous reductive elimination of fluorophosphonium cations. The resulting phosphine antimony(I) complexes catenate to give the first examples of cationic antimony bicyclic compounds, [(R₃P)₄Sb₆]⁴⁺, featuring a bicyclo[3.1.0]hexastibine framework stabilized by four phosphine ligands. The unprecedented 14‐electron redox process illustrates the generality of the reductive catenation method.     

Quantitative measurements of acoustic emissions from cavitation at the surface of a stone in response to a lithotripter shock wave

Measurements are presented of acoustic emissions from cavitation collapses on the surface of a synthetic kidney stone in response to shock waves (SWs) from an electrohydraulic lithotripter. A fiber optic probe hydrophone was used for pressure measurements, and passive cavitation detection was used to identify acoustic emissions from bubble collapse. At a lithotripter charging voltage of 20 kV, the focused SW incident on the stone surface resulted in a peak pressure of 43 +/- 6 MPa compared to 23 +/- 4 MPa in the free field. The focused SW incident upon the stone appeared to be enhanced due to the acoustic emissions from the forced cavitation collapse of the preexisting bubbles. The peak pressure of the acoustic emission from a bubble collapse was 34 +/- 15 MPa, that is, the same magnitude as the SWs incident on the stone. These data indicate that stresses induced by focused SWs and cavitation collapses are similar in magnitude thus likely play a similar role in stone fragmentation.     

On the SIG-Dimension of Trees Under the L ∞-Metric

Let ${{\mathcal P},}$ where ${|{\mathcal P}| \geq 2,}$ be a set of points in d-dimensional space with a given metric ρ. For a point ${p \in {\mathcal P},}$ let r _p be the distance of p with respect to ρ from its nearest neighbor in ${{\mathcal P}.}$ Let B(p,r _p ) be the open ball with respect to ρ centered at p and having the radius r _p . We define the sphere-of-influence graph (SIG) of ${{\mathcal P}}$ as the intersection graph of the family of sets ${\{B(p,r_p)\ | \ p\in {\mathcal P}\}.}$ Given a graph G, a set of points ${{\mathcal P}_G}$ in d-dimensional space with the metric ρ is called a d-dimensional SIG-representation of G, if G is isomorphic to the SIG of ${{\mathcal P}_G.}$ It is known that the absence of isolated vertices is a necessary and sufficient condition for a graph to have a SIG-representation under the L _∞-metric in some space of finite dimension. The SIG-dimension under the L _∞-metric of a graph G without isolated vertices is defined to be the minimum positive integer d such that G has a d-dimensional SIG-representation under the L _∞-metric. It is denoted by SIG _∞(G). We study the SIG-dimension of trees under the L _∞-metric and almost completely answer an open problem posed by Michael and Quint (Discrete Appl Math 127:447–460, 2003). Let T be a tree with at least two vertices. For each ${v\in V(T),}$ let leaf-degree(v) denote the number of neighbors of v that are leaves. We define the maximum leaf-degree as ${\alpha(T) = \max_{x \in V(T)}}$ leaf-degree(x). Let ${ S = \{v\in V(T)\|\}}$ leaf-degree{(v) = α}. If |S| = 1, we define β(T) = α(T) ? 1. Otherwise define β(T) = α(T). We show that for a tree ${T, SIG_\infty(T) = \lceil \log_2(\beta + 2)\rceil}$ where β = β (T), provided β is not of the form 2 ^k ? 1, for some positive integer k ≥ 1. If β = 2 ^k ? 1, then ${SIG_\infty (T) \in \{k, k+1\}.}$ We show that both values are possible.     

A Redox‐Confused Bismuth(I/III) Triamide with a T‐Shaped Planar Ground State

Reaction of a tethered triamine ligand with Bi(NMe₂)₃ gives a Bi triamide, for which a Bi^I electronic structure is shown to be most appropriate. The T‐shaped geometry at bismuth provides the first structural model for edge inversion in bismuthines and the only example of a planar geometry for pnictogen triamides. Analogous phosphorus compounds exhibit a distorted pyramidal geometry because of different Bi?N and P?N bond polarities. Although considerable Bi^I character is indicated for the title Bi triamide, it exhibits reactivity similar to Bi^III electrophiles, and expresses either a vacant or a filled p orbital at Bi, as evidenced by coordination of either pyridine N‐oxide or W(CO)₅. The product of the former shows evidence of coordination‐induced oxidation state change at bismuth.     

Hydrostibination

A rigid naphthalenediamine framework has been used to prepare antimony hydrides that feature LUMO shapes and energies similar to those found in secondary boranes. By exploiting this feature, we introduce the first examples of uncatalyzed hydrostibination reactions of robust C≡C, C=C, C=O, and N=N bonds as new elementary hydrometalation reactions analogous to hydroboration. These results endorse the notion of a diagonal relationship between the lightest p‐block element and the heaviest Group 15 elements and may lead to the conception of novel reaction chemistry.     

Transfer measurements for the Ti+Ni systems at near barrier energies

Large enhancements have been observed in the sub-barrier fusion cross sections for Ti+Ni systems in our previous studies. Coupled channel calculations incorporating couplings to 2⁺ and 3⁻ states failed to explain these enhancements completely. A possibilty of transfer channels contributing to the residual enhancements had been suggested. In order to investigate the role of relevant transfer channels, measurements of one- and two-nucleon transfer were carried out for ^46,48Ti+⁶¹Ni systems. The present paper gives the results of these studies.     

Hydrostibination of Alkynes: A Radical Mechanism**

The addition of Sb−H bonds to alkynes was reported recently as a new hydroelementation reaction that exclusively yields anti-Markovnikov Z-olefins from terminal acetylenes. We examine four possible mechanisms that are consistent with the observed stereochemical and regiochemical outcomes. A comprehensive analysis of solvent, substituent, isotope, additive, and temperature effects on hydrostibination reaction rates definitively refutes three ionic mechanisms involving closed-shell charged intermediates. Instead the data support a fourth pathway featuring open-shell neutral intermediates. Density-functional theory (DFT) calculations are consistent with this model, predicting an activation barrier that is in agreement with the experimental value (Eyring analysis) and a rate limiting step that is congruent with the experimental kinetic isotope effect. We therefore conclude that hydrostibination of arylacetylenes is initiated by the generation of stibinyl radicals, which then participate in a cycle featuring Sb^II and Sb^III intermediates to yield the observed Z-olefins as products. This mechanistic understanding will enable rational evolution of hydrostibination as a synthetic methodology.