The elusive 16-electron Cp*M(NO)Me(2)(M = Mo, W) complexes and their spontaneous conversions to Cp*M(NMe)(O)Me isomers.

Treatment of [Cp*Mo(NO)Cl(mu-Cl)](2) with magnesium (Me(2)Mg.dioxane, MeMgCl) or aluminum (Me(3)Al) methylating reagents affords the known compound [Cp*Mo(NO)Me(mu-Cl)](2) (1). Similar treatment of the dichloro precursor with MeLi in ethereal solvents generates an equimolar mixture of 1 and the trimethyl "ate" complex, Cp*MoMe(3)(NO-Li(OEt(2)(n)), (2-Et(2)O). Reaction of 2-Et(2)O with a source of [Me](+) forms Cp*MoMe(3)(=N-OMe)(3), a rare terminal alkoxylimido complex. Metathesis of the chloro ligands of [Cp*Mo(NO)Cl(mu-Cl)](2) by MeLi in toluene at low temperatures produces the target dimethyl complex, Cp*Mo(NO)Me(2) (4), in 75% isolated yield. In solution, 4 is predominantly a monomeric species, whereas in the solid state it adopts a dimeric or oligomeric structure containing isonitrosyl bridges as indicated by IR and (15)N/(13)C NMR spectroscopies. Hydrolysis of 4 affords meso- and rac-[Cp*Mo(NO)Me](2)(mu-O) (5), and the reactions of 4 with a range of Lewis bases, L, to form the 18e adducts Cp*Mo(NO)(L)Me(2) (e.g., Cp*Mo(NO)(PMe(3))Me(2) (7)), have established it to be the most electrophilic complex of its family. Acidolysis of the methyl groups of 4 is also facile. Most notably, 4 is thermally unstable in solution and undergoes isomerization via nitrosyl N-O bond cleavage to its oxo(imido) form, Cp*Mo(NMe)(O)Me (11), which is isolable from the final reaction mixture as the mu-oxo-bridged adduct formed by 4 and 11, i.e., Cp*Mo(NO)Me(2)(mu-O)Cp*Mo(NMe)Me (4 <-- 11). The rate of this isomerization is significantly faster for the tungsten dimethyl complex; hence, Cp*W(NO)Me(2) (12) is not isolable free of a supporting donor interaction and can only be isolated as Cp*W(NO)Me(2)(mu-O)Cp*W(NMe)Me (12 <-- 13) or Cp*W(NO)Me(2)(PMe(3)) (14) adducts.     

A conservative formulation for plasticity

In this paper we propose a fully conservative form for the continuum equations governing rate-dependent and rate-independent plastic flow in metals. The conservation laws are valid for discontinuous as well as smooth solutions. In the rate-dependent case, the evolution equations are in divergence form, with the plastic strain being passively convected and augmented by source terms. In the rate-independent case, the conservation laws involve a Lagrange multiplier that is determined by a set of constraints; we show that Riemann problems for this system admit scale-invariant solutions.     

Nuclear magnetic relaxation study of the establishment of order in the ammonium halides

The temperature dependence and thermal hysteresis of proton and deuteron spin—lattice relaxation times at high fields and a study of the recovery of the proton and deuteron magnetizations in ammonium halides are reported. The anomalies occurring near the order—disorder phase transition are related to structural, dielectric and Raman data. The hysteresis effect and the establishment of long range order are shown to be related.     

An improved solid-state perchlorate-selective electrode

A solid-state perchlorate sensitive electrode, based upon a radical-ion salt derived from N-ethylbenzothiazole-2,2'-azine. has been prepared. Its response characteristics and high apparent selectivity for perchlorate over many common anions show marked improvements with respect to similar systems which were studied earlier. The general electrode properties observed suggest that it may be considered an acceptable practical alternative to existing liquid-membrane sensors for perchlorate.     

Application of photon-counting in atomic-absorption spectrophotometry

An analysis is given of the statistics of photon-counting as a means of making measurements in atomic-absorption spectrometry. It is concluded that the simple application of Poisson counting statistics may give an over-optimistic estimate of the error, since other sources of error, such as flame flicker and variable nebulization rate, may be more significant.