Reactivity of [Fe4S4(SR)4]2-,3- clusters with sulfonium cations: analogue reaction systems for the initial step in biotin synthase catalysis

The first step in catalysis by a class of iron-sulfur enzymes that includes biotin synthase is the one-electron reductive cleavage of the obligatory cofactor S-adenosylmethionine by an [Fe(4)S(4)](+) cluster to afford methionine and the deoxyadenosyl radical (DOA*). To provide detailed information about the reactions of sulfonium ions with [Fe(4)S(4)](2+,+) clusters, the analogue reaction systems [Fe(4)S(4)(SR')(4)](2)(-)(,3)(-)/[PhMeSCH(2)R](+) (R' = Et (4, 6), Ph (5, 7); R = H (8), COPh (9), p-C(6)H(4)CN (10)) were examined by (1)H NMR spectroscopy. Sulfonium ions 8-10 react completely with oxidized clusters 4 and 5 to afford PhSMe and R'SCH(2)R in equimolar amounts as a result of electrophilic attack by the sulfonium ion on cluster thiolate ligands. Reactions are also complete with reduced clusters 6 and 7 but afford, depending on the substrate, the additional products RCH(3) (R = PhCO, p-C(6)H(4)CN) and the ylid PhMeS=CHR or (p-NCC(6)H(4)CH(2))(2). Redox potentials of 9 and 10 allow electron transfer from 6 or 7. The reaction systems 6/9,10 and 7/9,10 exhibit two reaction pathways, reductive cleavage and electrophilic attack, in an ca. 4:1 ratio inferred from product distribution. Cleavage is a two-electron process and, for example in the system 6/9, is described by the overall reaction 2[Fe(4)S(4)(SR')(4)](3)(-) + 2[PhMeSCH(2)R](+) --> 2[Fe(4)S(4)(SR')(4)](2)(-) + PhSMe + RCH(3) + PhMeS=CHR. This and other reactions may be summarized as [PhMeSCH(2)R](+) + 2e(-) + H(+) --> PhSMe + RCH(3); proposed reaction sequences parallel those for electrochemical reduction of sulfonium ions. This work demonstrates the intrinsic ability of [Fe(4)S(4)](+) clusters with appropriate redox potentials to reductively cleave sulfonium substrates in overall two-electron reactions. The analogue systems differ from the enzymes in that DOA* is generated in a one-electron reduction and is sufficiently stabilized within the protein matrix to abstract a hydrogen atom from substrate or an amino acid residue in a succeeding step. In the present systems, the radical produced in the initial step of the reaction sequence, [Fe(4)S(4)(SR')(4)](3)(-) + [PhMeSCH(2)R](+) --> [Fe(4)S(4)(SR')(4)](2)(-) + PhSMe + RCH(2)*, is not stabilized and is quenched by reduction and protonation.     

Synthesis and Crystal Structures of Two Schiff Bases of 2-(Methylthio)aniline with Halogenated Salicylaldehydes

Abstract  

The crystal structures of the new compounds 5-bromo-N-[2-(methylthio)-phenyl]salicylaldimine (1), and 3,5-dichloro-N-[2-(methylthio)phenyl]salicylaldimine (2) were obtained by single crystal X-ray diffraction. Compound 1 crystallizes in the monoclinic space group P2₁/c with a = 14.1479(14) ?, b = 5.3058(3) ?, c = 19.104(3) ?; β = 106.218(10)°; and Z = 4. Compound 2 crystallizes in the triclinic space group $ P\bar{1} $ P\bar{1} with a = 11.2249(10) ?, b = 13.863(2) ?, c = 13.9055(9) ?; and α = 99.378(15)°, β = 102.866(7)°, γ = 91.375(11)°; and Z = 6. Details of the synthesis, structures, and spectroscopic properties of the new compounds are discussed.     

The tail behaviour of a random sum of subexponential random variables and vectors

Let $\left\{ X,X_{i},i=1,2,...\right\} $ denote independent positive random variables having common distribution function (d.f.) F(x) and, independent of X, let ν denote an integer valued random variable. Using X ₀=0, the random sum Z=∑ _i=0 ^ν X _i has d.f. $G(x)=\sum_{n=0}^{\infty }\Pr\{\nu =n\}F^{n\ast }(x)$ where F ^n?(x) denotes the n-fold convolution of F with itself. If F is subexponential, Kesten’s bound states that for each ε>0 we can find a constant K such that the inequality $$ 1-F^{n\ast }(x)\leq K(1+\varepsilon )^{n}(1-F(x))\, , \qquad n\geq 1,x\geq 0 \, , $$ holds. When F is subexponential and E(1 +ε) ^ν <∞, it is a standard result in risk theory that G(x) satisfies $$ 1 - G{\left( x \right)} \sim E{\left( \nu \right)}{\left( {1 - F{\left( x \right)}} \right)},\,\,x \to \infty \,\,{\left( * \right)} $$ In this paper, we show that (*) holds under weaker assumptions on ν and under stronger conditions on F. Stam (Adv. Appl. Prob. 5:308–327, 1973) considered the case where $ \overline{F}(x)=1-F(x)$ is regularly varying with index –α. He proved that if α>1 and $E{\left( {\nu ^{{\alpha + \varepsilon }} } \right)} < \infty $ , then relation (*) holds. For 0<α<1, it is sufficient that Eν<∞. In this paper we consider the case where $\overline{F}(x)$ is an O-regularly varying subexponential function. If the lower Matuszewska index $\beta (\overline{F})<-1$ , then the condition ${\text{E}}{\left( {\nu ^{{{\left| {\beta {\left( {\overline{F} } \right)}} \right|} + 1 + \varepsilon }} } \right)} < \infty$ is sufficient for (*). If $\beta (\overline{F} )>-1$ , then again Eν<∞ is sufficient. The proofs of the results rely on deriving bounds for the ratio $\overline{F^{n\ast }}(x)/\overline{F} (x)$ . In the paper, we also consider (*) in the special case where X is a positive stable random variable or has a compound Poisson distribution derived from such a random variable and, in this case, we show that for n≥2, the ratio $\overline{F^{n\ast }}(x)/\overline{F}(x)\uparrow n$ as x↑∞. In Section 3 of the paper, we briefly discuss an extension of Kesten’s inequality. In the final section of the paper, we discuss a multivariate analogue of (*).     

The absolute convergence of weighted sums of dependent sequences of random variables

Summary The sum a _n X _n of a weighted series of a sequence {X _n } of identically distributed (not necessarily independent) random variables (r.v.s.) is a.s. absolutely convergent if for some in 0<1, ¦a _n ¦ < and E¦X _n ¦ < ; if a _n =z ⁿ for some ¦z¦<1 then it suffices that E(log¦X _n ¦)₊<. Examples show that these sufficient conditions are not necessary. For mutually independent {X _n } necessary conditions can be given: the a.s. absolute convergence of X _n z ⁿ (all ¦z¦<1) then implies E(log¦X _n ¦)₊ < , while if the X _n are non-negative stable r.v.s. of index , ¦a _n X _n ¦< if and only if ¦a _n ¦ < .     

Spectroscopy of the ν5 band of CDF3 by heterodyne measurement of SMMW laser emission frequencies

Submillimeter wave laser action has been previously reported in deuterated fluoroform (CDF₃) which is optically pumped by a CO₂ laser. In this paper, accurate frequency measurements are reported for 23 laser emissions. Of these lines, 21 can be assigned to the ν₅ degenerate vibrational state. The data were fitted with a theoretical expression for the transitions containing terms up to sixth order in J and K and also containing all important doubling effects. The quality of the fit was very good, yielding accurate values for many of the molecular constants of the ν₅ state.     

Spin-rotation measurements in π−p → K0Λ

The first measurements of spin-rotation in meson-baryon scattering in the resonance region are presented. These measurements, for the reaction π^?p → K⁰Λ, confirm the main predictions of a previous partial-wave analysis. Comments are made on resonant couplings in the reaction π^?p → K⁰Λ.     

The Phosphinoboration Reaction

The synthesis of phosphinoboronate esters containing a single P? B bond is reported, together with preliminary reactivity studies towards a range of organic substrates. These compounds add readily to aldehydes, ketones, aldimines, and α,β‐unsaturated enones to give primarily the corresponding 1,2‐addition products containing a new P? C bond. The first examples of transition‐metal‐catalyzed phosphinoborations of C‐C multiple bonds in which P? C and B? C bonds are formed in a single step are also disclosed; allenes react by a highly regioselective 1,2‐addition whereas terminal alkynes undergo a formal 1,1‐addition.