Enantioselective organic syntheses using chiral transition metal complexes V. (2S,3S)-Bis(dibenzophospholyl)butane, a rigid (S,S)-CHIRAPHOS analog

The P–Ph cleavage of phenyldibenzophosphole (1) with lithium in THF gives lithium dibenzophospholide (2). Reaction of 2 with ethyleneglycol ditosylate produces the known chelate ligand 1,2-bis(dibenzophospholyl)ethane (3) in good yield. Similarly, 2 and (2R,3R)-butanediol ditosylate give the new chiral chelate ligand (2S,3S)-bis(dibenzophospholyl)butane (4). Ligand exchange of [CpRu(PPh₃)₂Cl] with 3 or 4 yields the halfsandwich complexes [CpRu(C₁₂H₈PC₂H₄PC₁₂H₈)Cl] (5) and [CpRu((S,S)-C₁₂H₈PCHMeCHMePC₁₂H₈)Cl] (6). Complex 6 was characterized crystallographically (monoclinic, space group P2₁ (no. 4), a=820.6(4), b=1501.0(3), c=1172.8(6) pm, β=108.87(2)°, V=1.367(1)×10⁹ pm³, Z=2). The most conspicuous feature of the structure of 6 is the perfect coplanarity of the two dibenzophosphole moieties imposed by their steric interaction with the Cp ligand. Complex 6 and the thiophene complex [CpRu((S,S)-C₁₂H₈PCHMeCHMePC₁₂H₈)(SC₄H₄)]BF₄ (7) derived therefrom are remarkably unreactive with regard to ligand substitutions. A possible explanation is the lack of intramolecular

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–C stabilization en route to the transition state of ligand substitution. The enantiomeric purity of 6 and 7 could nevertheless be demonstrated by conversion to diastereomerically pure [CpRu((S,S)-C₁₂H₈PCHMeCHMePC₁₂H₈)((S)-CNCHMePh)]BF₄ (8).     

Pseudorapidity distributions of charged particles from Au + Au collisions at the maximum RHIC energy,square root[s(NN)] = 200 GeV

We present charged-particle multiplicities as a function of pseudorapidity and collision centrality for the 197Au+197Au reaction at square root[s(NN)] = 200 GeV. For the 5% most central events we obtain dN(ch)/deta/(eta = 0) = 625+/-55 and N(ch)/(-4.7< or =eta < or =4.7) = 4630 +/- 370, i.e., 14% and 21% increases, respectively, relative to square root[s(NN)] = 130 GeV collisions. Charged-particle production per pair of participant nucleons is found to increase from peripheral to central collisions around midrapidity. These results constrain current models of particle production at the highest RHIC energy.     

Observation of a motional Stark effect to determine the second-order Doppler effect

The high resolution two-photon spectroscopy of hydrogen is often limited by the second-order Doppler effect. To determine this effect, we apply a magnetic field perpendicular to the atomic beam. This field induces a quadratic motional Stark shift proportional, as the second-order Doppler effect, to v(2) (v atomic velocity). For some magnetic field, these two effects are opposite and the total shift due to the atomic velocity is reduced. We present the first observation of this effect for the 1S-3S transition in hydrogen.     

Rapidity dependence of charged antihadron to hadron ratios in Au+Au collisions at sqrt[s(NN)]=200 GeV

We present ratios of the numbers of charged antihadrons to hadrons (pions, kaons, and protons) in Au+Au collisions at sqrt[s(NN)]=200 GeV as a function of rapidity in the range y=0-3. While the ratios at midrapidity are approaching unity, the K(-)/K(+) and p;/p ratios decrease significantly at forward rapidities. An interpretation of the results within the statistical model indicates a reduction of the baryon chemical potential from mu(B) approximately 130 MeV at y=3 to mu(B) approximately 25 MeV at y=0.     

Light-particle emission in the reactions of 16O with Ti

Inclusive energy spectra and angular distributions for heavy ions $\text{(Z ≧ 3)}$ produced in the reactions of 227 MeV and 310 MeV ¹⁶O with Ti were measured. Also measured at the projectile energy of 310 MeV were energy and angular correlations between light charged particles (Z ≦ 2) and heavy ions. From comparisons with statistical model calculations upper limits to the complete fusion cross sections of 647 mb and 265 mb were derived for projectile energies of 227 MeV and 310 MeV, respectively. At 310 MeV the cross section of incomplete fusion processes was estimated to be over 505 mb. Emission of fast, high-energy α-particles and protons was observed to be a characteristic feature of quasi-elastic, deep-inelastic and fusion-like reactions. Average multiplicities of fast light particles in coincidence with heavy ions at +20° and +40° were estimated to be of the order of 1. The prompt emission of light appears to be the principal mechanism which limits complete fusion. A second component of α-particles observed in coincidence with deep-inelastic projectile-like fragments and having an energy comparable to Coulomb energies of particles emitted from target-like and projectile-like fragments appears as an excess yield in the direction of the recoiling target-like fragments. This component cannot be accounted for in terms of sequential emission processes and may result from a mechanism other than the one which leads to fast particle emission.     

One and Two Photon Excitation of Radiofrequency Trapped Ca+

射频囚禁离子被广泛应用于量子信息和冷分子制备. 对于从单个离子到10^6个离子不等的样品,这些原子的内能和外能可以被控制到非常高的精度. 重点讨论了利用射频囚禁的Ca+来作为频率计量的标准方法.     

Synthesis of Methyl 2-Acetamido-4,6-di-O-acetyl-3-S-acetyl-2-deoxy-3-thio-α-D-mannopyranoside

Methyl-2-acetamido-4,6-di-O-acetyl-3-S-acetyl-2-deoxy-3-thio-α-D-mannopy-ranoside has been synthesized by conversion of methyl 2-amino-2-deoxy-4,6-O-benzylidene-α-D-altropyranoside into the corresponding 3-O-methanesulfony1-2-N-[(methylthio)thiocarbonyl]derivative followed by intramolecular displacement of the 3-O-methanesulfonyloxy group with the (methylthio)thiocarbamoyl group.