Measurements of extinct fission products in nuclear bomb debris: Determination of the yield of the Trinity nuclear test 70 y later.

This paper describes an approach to measuring extinct fission products that would allow for the characterization of a nuclear test at any time. The isotopic composition of molybdenum in five samples of glassy debris from the 1945 Trinity nuclear test has been measured. Nonnatural molybdenum isotopic compositions were observed, reflecting an input from the decay of the short-lived fission products (95)Zr and (97)Zr. By measuring both the perturbation of the (95)Mo/(96)Mo and (97)Mo/(96)Mo isotopic ratios and the total amount of molybdenum in the Trinity nuclear debris samples, it is possible to calculate the original concentrations of the (95)Zr and (97)Zr isotopes formed in the nuclear detonation. Together with a determination of the amount of plutonium in the debris, these measurements of extinct fission products allow for new estimates of the efficiency and yield of the historic Trinity test.

Synthesis and reactivity of oxo-peroxo-vanadium(V) bipyridine compounds.

The vanadium(IV) compound [V(IV)O(OH)((t)Bu(2)bpy)(2)]BF(4) (V(IV)O(OH)) ((t)Bu(2)bpy = 4,4'-di-tert-butylbipyridine) is slowly oxidized by O(2) in ethereal solvents to give the oxo-peroxo compound [V(V)O(O(2))((t)Bu(2)bpy)(2)]BF(4) (V(V)O(O(2))) in excellent yield. This and related compounds were fully characterized by NMR, IR, and optical spectroscopies; mass spectrometry; elemental analyses; and an X-ray crystal structure of the 4,4'-dimethylbipyridine analog, [V(V)O(O(2))(Me(2)bpy)(2)]BF(4). Monitoring the reaction of V(IV)O(OH) with O(2) in THF/acetonitrile mixtures by (1)H NMR and optical spectroscopies surprisingly shows that the initial product is the cis-dioxo compound [V(V)(O)(2)((t)Bu(2)bpy)(2)]BF(4) (V(V)O(2)), which then converts to V(V)O(O(2)). Reaction of V(IV)O(OH) with (18)O(2) gives ca. 60% triply (18)O labeled V(V)O(O(2)). The mechanism of formation of V(V)O(O(2)) is complex and may occur via initial reduction of O(2) at vanadium(IV) to give a superoxo-vanadium(V) intermediate, autoxidation of the THF solvent, or both. That V(V)O(2) is generated first appears to be due to the ability of V(IV)O(OH) to act as a hydrogen atom donor. For instance, V(IV)O(OH) reacts with V(V)O(O(2)) to give V(V)O(2). V(V)O(O(2)) is also slowly reduced to V(IV)O(OH) by the organic hydrogen atom donors hydroquinone and TEMPOH (2,2,6,6-tetramethylpiperidin-1-ol) as well as by triphenylphosphine. Notably, the peroxo complex V(V)O(O(2)) is much less reactive with these substrates than the analogous dioxo compound V(V)O(2).

Slow hydrogen atom transfer reactions of oxo- and hydroxo-vanadium compounds: the importance of intrinsic barriers.

Reactions are described that interconvert vanadium(IV) oxo-hydroxo complexes [V(IV)O(OH)(R(2)bpy)(2)]BF(4) (1a-c) and vanadium(V) dioxo complexes [V(V)O(2)(R(2)bpy)(2)]BF(4) (2a-c) [R(2)bpy = 4,4'-di-tert-butyl-2,2'-bipyridine ((t)Bu(2)bpy), a; 4,4'-dimethyl-2,2'-bipyridine (Me(2)bpy), b; 2,2'-bipyridine (bpy), c]. These are rare examples of pairs of isolated, sterically unencumbered, first-row metal-oxo/hydroxo complexes that differ by a hydrogen atom (H(+) + e(-)). The V(IV)-(t)Bu(2)bpy derivative 1a has a useful (1)H NMR spectrum, despite being paramagnetic. Complex 2a abstracts H(*) from organic substrates with weak O-H and C-H bonds, converting 2,6-(t)Bu(2)-4-MeO-C(6)H(2)OH (ArOH) and 2,2,6,6-tetramethyl-N-hydroxypiperidine (TEMPOH) to their corresponding radicals ArO(*) and TEMPO, hydroquinone to benzoquinone, and dihydroanthracene to anthracene. The equilibrium constant for 2a + ArOH <==> 1a + ArO(*) is (4 +/- 2) x 10(-3), implying that the VO-H bond dissociation free energy (BDFE) is 70.6 +/- 1.2 kcal mol(-1). Consistent with this value, 1a is oxidized by 2,4,6-(t)Bu(3)C(6)H(2)O(*). All of these reactions are surprisingly slow, typically occurring over hours at ambient temperatures. The net hydrogen-atom pseudo-self-exchange 1a + 2b <==> 2a + 1b, using the (t)Bu- and Me-bpy substituents as labels, also occurs slowly, with k(se) = 1.3 x 10(-2) M(-1) s(-1) at 298 K, DeltaH(double dagger) = 15 +/- 2 kcal mol(-1), and DeltaS(double dagger) = 16 +/- 5 cal mol(-1) K. Using this k(se) and the BDFE, the vanadium reactions are shown to follow the Marcus cross relation moderately well, with calculated rate constants within 10(2) of the observed values. The vanadium self-exchange reaction is ca. 10(6) slower than that for the related Ru(IV)O(py)(bpy)(2)(2+)/Ru(III)OH(py)(bpy)(2)(2+) self-exchange. The origin of this dramatic difference has been probed with DFT calculations on the self-exchange reactions of 1c + 2c and on monocationic ruthenium complexes with pyrrolate or fluoride in place of the py ligands. The calculations reproduce the difference in barrier heights and show that transfer of a hydrogen atom involves more structural reorganization for vanadium than the Ru analogues. The vanadium complexes have larger changes in the metal-oxo and metal-hydroxo bond lengths, which is traced to the difference in d-orbital occupancy in the two systems. This study thus highlights the importance of intrinsic barriers in the transfer of a hydrogen atom, in addition to the thermochemical (bond strength) factors that have been previously emphasized.