Venancio Rodrı́guez

Universidad de Murcia

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José Ruiz

Universidad de Murcia

G. López

Comillas Pontifical University

N. Cutillas

Universidad de Murcia

Christoph Janiak

Heinrich Heine University Düsseldorf

José Pérez

Universidad Politécnica de Cartagena

Penny A. Chaloner

University of Sussex

Ana Zamora

KU Leuven

Enrique Ortega

Universidad de Murcia

Joaquı́m Ruiz

Universidad Científica del Sur

C. De Haro

Universidad de Murcia

Cooperative Institutions

Universidad de Murcia

Centre National de la Recherche Scientifique

Universitat de Barcelona

Universitat Autònoma de Barcelona

Consejo Superior de Investigaciones Científicas

Instituto Murciano de Investigación Biosanitaria

Laboratoire de Chimie de Coordination

Universitat de València

Université Toulouse III - Paul Sabatier

Universidad de Granada

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Palladium(ii) complexes with pentafluorophenyl ligands: structures, C6F5 fluxionality by 2D-NMR studies and pre-catalysts for the vinyl addition polymerization of norbornene

Dalton Transactions (2010)

Frederik Blank Harald Scherer José Ruiz Venancio Rodrı́guez Christoph Janiak

The palladium(II) complex [Pd(C6F5)Cl(bpzm*)] (5) [bpzm* = bis(3,5-dimethylpyrazol-1-yl)methane] was characterized by 1H,1H-TOCSY, 1H-NOE difference spectra, 1H,19F-HOESY and 13C,1H-HMBC 2D-NMR techniques. Chemical exchange of the methylene protons from 1H,1H-NOESY cross peaks and exchange of the ortho- and meta-fluorine atoms, respectively, from 19F,19F-EXSY cross peaks indicates that the Pd-bpzm* chelate ring boat-to-boat inversion occurs at a rate slower than the NMR time scale together with a concomitant change of the C6F5 atom positions. The presence of three 19F-NMR signals for 2Fo : 1Fp : 2Fm of the C6F5 ligand for complexes [Pd(C6F5)Cl(tmeda)] (1) and [Pd(C6F5)Cl(bipy)] (3) (tmeda = N,N,N′,N′-tetramethylethylenediamine; bipy = 2,2′-bipyridine) is interpreted as being due to identical hemi-spaces above and below an apparent symmetry plane coinciding with the Pd-coordination plane instead of free ring rotation. The molecular structures of 1, 3 and 5 from single-crystal studies suggest that the hindered C6F5 rotation is not limited to 5 but is also present in 1 and 3 due to ligand repulsion. Complexes [Pd(C6F5)Cl(tmeda)] (1), [Pd(C6F5)OH(tmeda)] (2), [Pd(C6F5)Cl(bipy)] (3), [Pd(C6F5)OH(bipy)] (4) and [Pd(C6F5)Cl(bpzm*)] (5) have been applied as pre-catalysts for the vinyl homopolymerization of norbornene in combination with the cocatalyst methylaluminoxane (MAO). Activities of more than 106 gpolymer/(molPd h) could be reached with these catalytic systems. Based on the spectrochemical series, pre-catalysts 1 and 2 with the pure σ-donor and more weakly bound aliphatic amine ligands showed higher polymerization activities than compounds 3–5 with modest π-accepting and stronger bound aromatic substituents. This is reasoned with a kinetic activation effect through a faster removal of the more weakly bound ligands upon reaction with MAO together with the chloro or hydroxo ligands to give the active, almost "naked" Pd2+ cations. For the activation mechanism, 1H-, 13C- and 19F-NMR studies of the MAO activated complex 5 showed about 13% chlorine-to-methyl exchange for a molar Pd : Al ratio of 1 : 10. For 5 : MAO at a Pd : Al ratio of 1 : 100 abstraction of C6F5 takes place with a redox reaction giving Pd metal and C6F5-CH3 in the absence of norbornene monomer.

Norbornene

10.1039/b925674a

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Citations (38)

CCDC 227318: Experimental Crystal Structure Determination

The Cambridge Structural Database (2004)

Joaquı́m Ruiz M.T. Martínez F. Florenciano Venancio Rodrı́guez G. López

An entry from the Cambridge Structural Database, the world’s repository for small molecule crystal structures. The entry contains experimental data from a crystal diffraction study. The deposited dataset for this entry is freely available from the CCDC and typically includes 3D coordinates, cell parameters, space group, experimental conditions and quality measures.

10.5517/cc7mjv6

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CCDC 784452: Experimental Crystal Structure Determination

The Cambridge Structural Database (2011)

D. Cantillo M. Avalos Reyes Babiano P. Cintas J. L. Jiménez

10.5517/ccvb8xb

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CCDC 2007158: Experimental Crystal Structure Determination

The Cambridge Structural Database (2021)

Enrique Ortega Cristina Pérez-Arnáiz Venancio Rodrı́guez Christoph Janiak Natalia Busto

10.5517/ccdc.csd.cc25cm17

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Novel β-iminoenolato (or β-carbonyliminato) complexes starting from di-μ-hydroxo palladium or platinum complexes with dimethyl acetylenedicarboxylate and primary amines: Crystal structure of

Journal of Organometallic Chemistry (1996)

José Ruiz Venancio Rodrı́guez G. López Penny A. Chaloner Peter B. Hitchcock

Dimethyl acetylenedicarboxylate

10.1016/0022-328x(96)06339-5

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From Behind the Shadows of Great Musical Figures: Marie Mennessier-Nodier: A composer in Nineteenth-Century Microhistory

Bulletin of the Transilvania University of Braşov Series VIII Performing Arts (2025)

Venancio Rodrı́guez

Within the history of music, the scholarship on the great female figures from across all time periods—most notably composers, performers, patrons, and teachers—continues to grow. In addition to these notable individuals, however, there were numerous anonymous women, most often associated with musical teaching or private performances in the European salons, who achieved a prominent place in their society. In this work, I propose to address this with an approach to the case of the lesser-known composer and poet Marie Mennessier-Nodier (1811–1893). Following a review of the place of women musicians in current academic research, I delve into the life and the legacy of Marie Mennessier-Nodier, as well as her place in the musical context in which she lived: nineteenth-century French Romanticism. Ultimately, the research on Marie Mennessier-Nodier allows us to reflect on the women who, despite their exclusion from the ‘great history’, were nevertheless important in shaping new generations of musicians and the artistic life of their context.

Microhistory

10.31926/but.pa.2024.17.66.3.28

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Can a single C–H⋯F–C hydrogen bond make a difference? Assessing the H⋯F bond strength from 2-D¹H-¹⁹F CP/MAS NMR

CrystEngComm (2006)

Gerhard Althoff José Ruiz Venancio Rodrı́guez G. López José Pérez

Contrary to common belief a single C–H⋯F–C contact in [(η5-C5H5)Pd(C6F5)(PPh3)] is strong enough to pair two independent molecules and render them crystallographically different as suggested by its strongest 1H–19F dipole–dipole coupling in a 2-D CP/MAS PILGRIM NMR experiment together with solid state 1-D 19F{1H} and 2-D 19F RFDR NMR spectroscopy – thereby proving the power of 2-D solid-state NMR for assessing the strength of supramolecular contacts.

J-coupling

Magnetic dipole–dipole interaction

Carbon-13 NMR satellite

10.1039/b610718b

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Citations (66)

CCDC 221936: Experimental Crystal Structure Determination

The Cambridge Structural Database (2004)

Juan Manuel García‐Ruiz Venancio Rodrı́guez A. Perez G. López D. Bautista

10.5517/cc7fy7t

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