4-Cyanopyridine and amide-N and amide-O linkage isomers of 4-pyridinecarboxamide on trans-chloro(1,4,8,11-tetraazacyclotetradecane)ruthenium(II/III)

The synthesis, UV-vis spectra, and electrochemical behavior of the nitrile-bonded trans-[Ru(II)Cl(cyclam)(4-NCpyH(+))](BF(4))(2) (4-Ncpy = 4-cyanopyridine; cyclam = 1,4,8,11-tetraazacyclotetradecane) and of trans-[Ru(III)Cl(cyclam)(NHC(O)-4-pyH(+))](2+) are described. The UV-vis spectrum of the Ru(II) nitrile complex shows a MLCT band at 548 nm at pH 1, which is shifted to 440 nm at pH approximately 6, for the unprotonated species. trans-[Ru(II)Cl(cyclam)(4-NCpyH(+))](2+) was electrolytically oxidized (+600 mV vs Ag/AgCl) at pH 1 to Ru(III), followed by hydrolysis (k = 0.25 s(-1)) of the coordinated nitrile to give trans-[Ru(III)Cl(cyclam)(NHC(O)-4-pyH(+))](2+), in which the amide is deprotonated and coordinated through nitrogen. The identity of the species is pH dependent, the nitrogen-bonded amide prevailing at low pH (< 7), but the oxygen-bonded amide is formed through linkage isomerization at higher pH (>8). Reduction of trans-[Ru(III)Cl(cyclam)(NHC(O)-4-pyH)](2+) in acidic media does not result in fast aquation (k = approximately 2.4 x 10(-5) s(-1)) as for other amides on ruthenium(II) pentaammine, but instead linkage isomerization occurs, resulting in the oxygen-bonded species, with an estimated rate constant of approximately 2 x 10(-2) s(-1), smaller than in the pentaammine analogues.     

Fluorine in medicinal chemistry

It has become evident that fluorinated compounds have a remarkable record in medicinal chemistry and will play a continuing role in providing lead compounds for therapeutic applications. This tutorial review provides a sampling of renowned fluorinated drugs and their mode of action with a discussion clarifying the role and impact of fluorine substitution on drug potency.     

First observation of K{L}-->pi{+/-}e{-/+}nue{+}e{-}

This Letter is the first report of the K{L}-->pi{+/-}e{-/+}nue{+}e{-} decay. Based on 19 208+/-144 events, we determine the branching fraction, B(K{L}-->pi{+/-}e{-/+}nue{+}e{-}M_{e{+}e{-}}>5 MeV/c{2},E{e{+}e{-}}{*}>30 MeV)=(1.285+/-0.041)x10{-5}, and Gamma(K{e3ee}M{e{+}e{-}}>5 MeV/c{2})/Gamma(K{e3})=[4.57+/-0.04(stat)+/-0.14(syst)]x10{-5}. This ratio agrees with a theoretical prediction based on chiral perturbation theory (ChPT) calculated to O(p{4}). The measured kinematical distributions agree with those predicted by just ChPT O(p{4}), but show significant disagreement with ones predicted by leading-order ChPT.     

Galois embedding problems with cyclic quotient of order<Emphasis Type="Italic">p</Emphasis>

LetK/F be a cyclic field extension of odd prime degree. We consider Galois embedding problems involving Galois groups with common quotient Gal(K/F) such that corresponding normal subgroups are indecomposable . For these embedding problems we prove conditions on solvability, formulas for explicit construction, and results on automatic realizability. Research supported in part by the Natural Sciences and Engineering Research Council of Canada grant R0370A01, as well as by the special Dean of Science Fund at the University of Western Ontario. Supported by the Mathematical Sciences Research Institute, Berkeley. Research supported in part by National Security Agency grant MDA904-02-1-0061.     

Brauer groups of genus zero extensions of number fields

We determine the isomorphism class of the Brauer groups of certain nonrational genus zero extensions of number fields. In particular, for all genus zero extensions of the rational numbers that are split by , .

     

Observation of the decay xi0 --> sigma+ mu- nu(mu)

The xi0 muon semileptonic decay has been observed for the first time with nine identified events using the KTeV beam line and detector at Fermilab. The decay is normalized to the xi0 beta decay mode and yields a value for the ratio of decay rates gamma(xi0 --> sigma+ mu- nu(mu))/gamma(xi0 --> sigma+ e- nu(e)) of [1.8(-0.5)(+0.7)(stat) +/- 0.2(syst)] x 10(-2). This is in agreement with the SU(3) flavor symmetric quark model.