Terminal Phosphanido Rhodium Complexes Mediating Catalytic P—P and P—C Bond Formation

Complexes with terminal phosphanido (M-PR2) functionalities are believed to be crucial intermediates in new catalytic processes involving the formation of P-P and P-C bonds. We showcase here the isolation and characterization of mononuclear phosphanide rhodium complexes ([RhTp(H)(PR2)L]) that result from the oxidative addition of secondary phosphanes, a reaction that was also explored computationally. These compounds are active catalysts for the dehydrocoupling of PHPh2 to Ph2P-PPh2. The hydrophosphination of dimethyl maleate and the unactivated olefin ethylene is also reported. Reliable evidence for the prominent role of mononuclear phosphanido rhodium species in these reactions is also provided.The generous financial support from MICINN/FEDER (Project CTQ2011-22516), Gobierno de Aragón/FSE (GA/FSE, Inorganic Molecular Architecture Group, E70), and NWO-CW (VICI project 016.122.613; BdB) is gratefully acknowledged. A.M.G. and A.L.S. thank Gobierno de Aragón and MEC, respectively, for fellowships.Peer reviewe

The Solar Neutrino Problem in the Light of a Violation of the Equivalence Principle

We have found that long-wavelength neutrino oscillations induced by a tiny breakdown of the weak equivalence principle of general relativity can provide a viable solution to the solar neutrino problem.Comment: 3 pages, 1 eps figure, Talk given by R. Zukanovich Funchal at the VIth International Workshop on ``Topics in Astroparticle and Underground Physics'' (TAUP99), Sep. 6-10, 1999, College de France, Paris - Franc

Rhodium complexes in p-C bond formation: Key role of a hydrido ligand

Olefin hydrophosphanation is an attractive route for the atom-economical synthesis of functionalized phosphanes. This reaction involves the formation of P-C and H-C bonds. Thus, complexes that contain both hydrido and phosphanido functionalities are of great interest for the development of effective and fast catalysts. Herein, we showcase the excellent activity of one of them, [Rh(Tp)H(PMe3)(PPh2)] (1), in the hydrophosphanation of a wide range of olefins. In addition to the required nucleophilicity of the phosphanido moiety to accomplish the P-C bond formation, the key role of the hydride ligand in 1 has been disclosed by both experimental results and DFT calculations. An additional Rh-H··· C stabilization in some intermediates or transition states favors the hydrogen transfer reaction from rhodium to carbon to form the H-C bond. Further support for our proposal arises from the poor activity exhibited by the related chloride complex [Rh(Tp)Cl(PMe3)(PPh2)] as well as from stoichiometric and kinetic studies

Hydrophosphination of Activated Alkenes by a Cobalt(I) Pincer Complex

Herein we report the synthesis of three heteroleptic first-row transition metal(II) complexes containing carbazolido NNN pincer ligands and conversion to the corresponding metal(I)-carbonyl complexes via a reductive carbonylation route. These complexes are precatalysts for the hydrophosphination of activated alkenes, affording a cobalt-catalysed hydrophosphination process that solely and selectively yields the ß addition (anti-Markovnikov) product. The scope of this transformation has been investigated using a variety of activated alkenes. Isolation and characterisation of substrate-coordinated intermediates reveal available coordination sites, which provide insight into the proposed catalytic cycle

Measuring CP violation and mass ordering in joint long baseline experiments with superbeams

We propose to measure the CP phase $\delta_{\rm CP}$, the magnitude of the neutrino mixing matrix element $|U_{e3}|$ and the sign of the atmopheric scale mass--squared difference $\Delta{\rm m}^2_{31}$ with a superbeam by the joint analysis of two different long baseline neutrino oscillation experiments. One is a long baseline experiment (LBL) at 300 km and the other is a very long baseline (VLBL) experiment at 2100 km. We take the neutrino source to be the approved high intensity proton synchrotron, HIPA. The neutrino beam for the LBL is the 2-degree off-axis superbeam and for the VLBL, a narrow band superbeam. Taking into account all possible errors, we evaluate the event rates required and the sensitivities that can be attained for the determination of $\delta_{\rm CP}$ and the sign of $\Delta m^2_{31}$. We arrive at a representative scenario for a reasonably precise probe of this part of the neutrino physics.Comment: 25 RevTEX pages, 16 PS figures, revised figure captions and references adde

Neutrino hierarchy from CP-blind observables with high density magnetized detectors

High density magnetized detectors are well suited to exploit the outstanding purity and intensities of novel neutrino sources like Neutrino Factories and Beta Beams. They can also provide independent measurements of leptonic mixing parameters through the observation of atmospheric muon-neutrinos. In this paper, we discuss the combination of these observables from a multi-kton iron detector and a high energy Beta Beam; in particular, we demonstrate that even with moderate detector granularities the neutrino mass hierarchy can be determined for $\theta_{13}$ values greater than 4$^\circ$.Comment: 16 pages, 7 figures. Added a new section discussing systematic errors (sec 5.2); sec.5.1 and 4 have been extended. Version to appear in EPJ

Short-Baseline Neutrino Oscillations at a Neutrino Factory

Within the framework of three-neutrino and four-neutrino scenarios that can describe the results of the LSND experiment, we consider the capabilities of short baseline neutrino oscillation experiments at a neutrino factory. We find that, when short baseline (L \alt 100 km) neutrino factory measurements are used together with other accelerator-based oscillation results, the complete three-neutrino parameter space can best be determined by measuring the rate of $\nu_e \to \nu_\tau$ oscillations, and measuring CP violation with either $\nu_e \to \nu_\mu$ or $\nu_\mu \to \nu_\tau$ oscillations (including the corresponding antineutrino channels). With measurements of CP violation in both $\nu_e \to \nu_\mu$ and $\nu_\mu \to \nu_\tau$ it may be possible to distinguish between the three- and four-neutrino cases.Comment: 16 pages, Revtex (single-spaced), 8 postscript figures, uses epsf.st

Long Baseline Neutrino Physics with a Muon Storage Ring Neutrino Source

We examine the physics capabilities of known flavor neutrino beams from intense muon sources. We find that long-baseline neutrino experiments based on such beams can provide precise measurements of neutrino oscillation mass and mixing parameters. Furthermore, they can test whether the dominant atmospheric neutrino oscillations are \nu_\mu --> \nu_\tau and/or \nu_\mu --> \nu_s, determine the \nu_\mu --> \nu_e content of atmospheric neutrino oscillations, and measure \nu_e --> \nu_\tau appearance. Depending on the oscillation parameters, they may be able to detect Earth matter and CP violation effects and to determine the ordering of some of the mass eigenstates.Comment: 38 pages, Revtex with epsf.sty, 21 postscript figures. Minor text revisions, some new numbers in Tables II and II

Confusing non-standard neutrino interactions with oscillations at a neutrino factory

Most neutrino mass theories contain non-standard interactions (NSI) of neutrinos which can be either non-universal (NU) or flavor-changing (FC). We study the impact of such interactions on the determination of neutrino mixing parameters at a neutrino factory using the so-called ``golden channels'' \pnu{e}\to\pnu{\mu} for the measurement of \theta_{13}. We show that a certain combination of FC interactions in neutrino source and earth matter can give exactly the same signal as oscillations arising due to \theta_{13}. This implies that information about \theta_{13} can only be obtained if bounds on NSI are available. Taking into account the existing bounds on FC interactions, this leads to a drastic loss in sensitivity in \theta_{13}, at least two orders of magnitude. A near detector at a neutrino factory offers the possibility to obtain stringent bounds on some NSI parameters. Such near site detector constitutes an essential ingredient of a neutrino factory and a necessary step towards the determination of \theta_{13} and subsequent study of leptonic CP violation.Comment: 23 pages, 5 figures, improved version, accepted for publication in Phs. Rev. D, references adde