A frustrated-Lewis-pair approach to catalytic reduction of alkynes to cis-alkenes

Frustrated Lewis pairs are compounds containing both Lewis acidic and Lewis basic moieties, where the formation of an adduct is prevented by steric hindrance. They are therefore highly reactive, and have been shown to be capable of heterolysis of molecular hydrogen, a property that has led to their use in hydrogenation reactions of polarized multiple bonds. Here, we describe a general approach to the hydrogenation of alkynes to cis-alkenes under mild conditions using the unique ansa-aminohydroborane as a catalyst. Our approach combines several reactions as the elementary steps of the catalytic cycle: hydroboration (substrate binding), heterolytic hydrogen splitting (typical frustrated-Lewis-pair reactivity) and facile intramolecular protodeborylation (product release). The mechanism is verified by experimental and computational studies

Replacing C6F5 groups with Cl and H atoms in frustrated Lewis pairs : H-2 additions and catalytic hydrogenations

2-(Dialkylamino) phenylboranes containing the BXZ group, where X, Z = C6F5, Cl, and H, were prepared in a few synthetic steps and demonstrated the cleavage of H-2 under mild conditions. Depending on the nature of the dialkylamino group, X, and Z, the stability of the produced zwitterionic H-2 adducts varies from isolated solids indefinitely stable in an inert atmosphere to those quickly equilibrating with the initial aminoborane and H-2. Using a combined experimental/computational approach on a series of isostructural aminoboranes (dialkylamino = 2,2,6,6-tetramethylpiperid-1-yl), it was demonstrated that the electro-negativity and the steric effect of the substituents generally follow the trend C6F5 similar to Cl >> H. This observation is useful for designing new FLPs for practical applications. As an example, we demonstrated the hydrogenation of alkynes to cis-alkenes under mild conditions that was catalyzed by a chloro-analogue of the C6F5-substituted aminoborane developed previously. The presence of a BHCl group in the amino-chloroboranes or in their H-2 adducts features facile redistribution of the H and Cl atoms and the formation of polychloro and polyhydrido species.Peer reviewe

Spontaneous N-15 Nuclear Spin Hyperpolarization in Metal-Free Activation of Parahydrogen by Molecular Tweezers

The ability of frustrated Lewis pairs (FLPs) to activate H-2 is of significant interest for metal-free catalysis. The activation of H-2 is also the key element of parahydrogen-induced polarization (PHIP), one of the nuclear spin hyper polarization techniques. It is demonstrated that o-phenylene-based ansa-aminoboranes (AABs) can produce H-1 nuclear spin hyperpolarization through a reversible interaction with parahydrogen at ambient temperatures. Heteronuclei are useful in NMR and MRI as well because they have a broad chemical shift range and long relaxation times and may act as background-free labels. We report spontaneous formation of N-15 hyperpolarization of the N-H site for a family of AABs. The process is efficient at the high magnetic field of an NMR magnet (7 T), and it provides up to 350-fold N-15 signal enhancements. Different hyperpolarization effects are observed with various AAB structures and in a broad temperature range. Spontaneous hyperpolarization, albeit an order of magnitude weaker than that for N-15, was also observed for B-11 nuclei.Peer reviewe

Heterolytic Scission of Hydrogen Within a Crystalline Frustrated Lewis Pair

We report the heterolysis of molecular hydrogen under ambient conditions by the crystalline frustrated Lewis pair (FLP) 1-{2-[bis (pentafluorophenyOboryl] phenyl -2, 2,6,6-tetrame-thylpiperidine (KCAT). The gas-solid reaction provides an approach to prepare the solvent-free, polycrystalline ion pair KCATH2 through a single crystal to single crystal transformation. The crystal lattice of KCATH2 increases in size relative to the parent KCAT by approximately 2%. Microscopy was used to follow the transformation of the highly colored red/orange KCAT to the colorless KCATH2 over a period of 2 h at 300 K under a flow of H-2 gas. There is no evidence of crystal decrepitation during hydrogen uptake. Inelastic neutron scattering employed over a temperature range from 4-200 K did not provide evidence for the formation of polarized H-2 in a precursor complex within the crystal at low temperatures and high pressures. However, at 300 K, the INS spectrum of KCAT transformed to the INS spectrum of KCATH2. Calculations suggest that the driving force is more favorable in the solid state compared to the solution or gas phase, but the addition of H-2 into the KCAT crystal is unfavorable. Ab Initio methods were used to calculate the INS spectra of KCAT, KCATH2, and a possible precursor complex of H-2 in the pocket between the B and N of crystalline KCAT. Ex-situ NMR showed that the transformation from KCAT to KCATH2 is quantitative and our results suggest that the hydrogen heterolysis process occurs via H-2 diffusion into the FLP crystal with a rate-limiting movement of H-2 from inactive positions to reactive sites.Peer reviewe

Impact of heterocirculene molecular symmetry upon two-dimensional

Peer reviewe

Cross sections and double-helicity asymmetries of midrapidity inclusive charged hadrons in p+p collisions at sqrt(s)=62.4 GeV

Unpolarized cross sections and double-helicity asymmetries of single-inclusive positive and negative charged hadrons at midrapidity from p+p collisions at sqrt(s)=62.4 GeV are presented. The PHENIX measurements for 1.0 < p_T < 4.5 GeV/c are consistent with perturbative QCD calculations at next-to-leading order in the strong coupling constant, alpha_s. Resummed pQCD calculations including terms with next-to-leading-log accuracy, yielding reduced theoretical uncertainties, also agree with the data. The double-helicity asymmetry, sensitive at leading order to the gluon polarization in a momentum-fraction range of 0.05 ~< x_gluon ~< 0.2, is consistent with recent global parameterizations disfavoring large gluon polarization.Comment: PHENIX Collaboration. 447 authors, 12 pages, 5 figures, 5 tables. Submitted to Physical Review

Inclusive cross section and single-transverse-spin asymmetry for very forward neutron production in polarized p+p collisions at sqrt(s)=200 GeV

The energy dependence of the single-transverse-spin asymmetry, A_N, and the cross section for neutron production at very forward angles were measured in the PHENIX experiment at RHIC for polarized p+p collisions at sqrt(s)=200 GeV. The neutrons were observed in forward detectors covering an angular range of up to 2.2 mrad. We report results for neutrons with momentum fraction of x_F=0.45 to 1.0. The energy dependence of the measured cross sections were consistent with x_F scaling, compared to measurements by an ISR experiment which measured neutron production in unpolarized p+p collisions at sqrt(s)=30.6--62.7 GeV. The cross sections for large x_F neutron production for p+p collisions, as well as those in e+p collisions measured at HERA, are described by a pion exchange mechanism. The observed forward neutron asymmetries were large, reaching A_N=-0.08+/-0.02 for x_F=0.8; the measured backward asymmetries, for negative x_F, were consistent with zero. The observed asymmetry for forward neutron production is discussed within the pion exchange framework, with interference between the spin-flip amplitude due to the pion exchange and nonflip amplitudes from all Reggeon exchanges. Within the pion exchange description, the measured neutron asymmetry is sensitive to the contribution of other Reggeon exchanges even for small amplitudes.Comment: 383 authors, 16 pages, 18 figures, 6 tables. Submitted to Phys. Rev. D. Plain text data tables for the points plotted in figures for this and previous PHENIX publications are (or will be) publicly available at http://www.phenix.bnl.gov/papers.htm

Upsilon (1S+2S+3S) production in d+Au and p+p collisions at sqrt(s_NN)=200 GeV and cold-nuclear matter effects

The three Upsilon states, Upsilon(1S+2S+3S), are measured in d+Au and p+p collisions at sqrt(s_NN)=200 GeV and rapidities 1.2<|y|<2.2 by the PHENIX experiment at the Relativistic Heavy-Ion Collider. Cross sections for the inclusive Upsilon(1S+2S+3S) production are obtained. The inclusive yields per binary collision for d+Au collisions relative to those in p+p collisions (R_dAu) are found to be 0.62 +/- 0.26 (stat) +/- 0.13 (syst) in the gold-going direction and 0.91 +/- 0.33 (stat) +/- 0.16 (syst) in the deuteron-going direction. The measured results are compared to a nuclear-shadowing model, EPS09 [JHEP 04, 065 (2009)], combined with a final-state breakup cross section, sigma_br, and compared to lower energy p+A results. We also compare the results to the PHENIX J/psi results [Phys. Rev. Lett. 107, 142301 (2011)]. The rapidity dependence of the observed Upsilon suppression is consistent with lower energy p+A measurements.Comment: 495 authors, 11 pages, 9 figures, 5 tables. Submitted to Phys. Rev. C. Plain text data tables for the points plotted in figures for this and previous PHENIX publications are (or will be) publicly available at http://www.phenix.bnl.gov/papers.htm

Event-by-event fluctuations in Mean pTp_T and Mean eTe_T in sqrt(s_NN) = 130 GeV Au+Au Collisions

Distributions of event-by-event fluctuations of the mean transverse momentum and mean transverse energy near mid-rapidity have been measured in Au+Au collisions at sqrt(s_NN) = 130 GeV at RHIC. By comparing the distributions to what is expected for statistically independent particle emission, the magnitude of non-statistical fluctuations in mean transverse momentum is determined to be consistent with zero. Also, no significant non-random fluctuations in mean transverse energy are observed. By constructing a fluctuation model with two event classes that preserve the mean and variance of the semi-inclusive p_T or e_T spectra, we exclude a region of fluctuations in sqrt(s_NN) = 130 GeV Au+Au collisions.Comment: 10 pages, RevTeX 3, 7 figures, 4 tables, 307 authors, submitted to Phys. Rev. C on 22 March 2002. Plain text data tables for the points plotted in figures for this and previous PHENIX publications are (will be made) publicly available at http://www.phenix.bnl.gov/phenix/WWW/run/phenix/papers.htm

Inclusive cross section and double helicity asymmetry for pi^0 production in p+p collisions at sqrt(s) = 62.4 GeV

The PHENIX experiment presents results from the RHIC 2006 run with polarized proton collisions at sqrt(s) = 62.4 GeV for inclusive pi^0 production at mid-rapidity. Unpolarized cross section results are measured for transverse momenta p_T = 0.5 to 7 GeV/c. Next-to-leading order perturbative quantum chromodynamics calculations are compared with the data, and while the calculations are consistent with the measurements, next-to-leading logarithmic corrections improve the agreement. Double helicity asymmetries A_LL are presented for p_T = 1 to 4 GeV/c and probe the higher range of Bjorken_x of the gluon (x_g) with better statistical precision than our previous measurements at sqrt(s)=200 GeV. These measurements are sensitive to the gluon polarization in the proton for 0.06 < x_g < 0.4.Comment: 387 authors from 63 institutions, 10 pages, 6 figures, 1 table. Submitted to Physical Review D. Plain text data tables for the points plotted in figures for this and previous PHENIX publications are (or will be) publicly available at http://www.phenix.bnl.gov/papers.htm