While it is widely recognized that purely organic molecular systems with multiple bonds undergo chemical condensation at sufficiently high pressures (from tenths to tens of GPa), the fate of organometallics at extreme conditions remains largely underexplored. We have investigated the high pressure (up to 41 GPa) chemical transformations in a simple molecular system known as nickelocene, (C5H5)2Ni, which serves as a representative example of a class of organometallics called sandwich compounds. Nickelocene decomposed above 13 GPa, at room temperature, while lower pressure thresholds have been observed at higher temperatures (295-573 K). The products were identified as nanocomposite materials, primarily composed of disordered, nickel-rich nanoparticles segregated within an extended, amorphous matrix of hydrogenated carbon (a-C:H). The investigation was conducted by means of diamond anvil cells in combination with optical spectroscopies and microscopy, synchrotron x-ray absorption spectroscopy and diffraction, as well as transmission electron microscopy. Our findings have the potential to stimulate further research into the high-pressure chemical reactivity of organometallics and open up new synthesis routes for the production of metal-based nanoparticles, which find a wide range of applications.

High pressure decomposition of a sandwich compound

Samuele Fanetti;Enrico Berretti;Roberto Bini;Mario Santoro
2023

Abstract

While it is widely recognized that purely organic molecular systems with multiple bonds undergo chemical condensation at sufficiently high pressures (from tenths to tens of GPa), the fate of organometallics at extreme conditions remains largely underexplored. We have investigated the high pressure (up to 41 GPa) chemical transformations in a simple molecular system known as nickelocene, (C5H5)2Ni, which serves as a representative example of a class of organometallics called sandwich compounds. Nickelocene decomposed above 13 GPa, at room temperature, while lower pressure thresholds have been observed at higher temperatures (295-573 K). The products were identified as nanocomposite materials, primarily composed of disordered, nickel-rich nanoparticles segregated within an extended, amorphous matrix of hydrogenated carbon (a-C:H). The investigation was conducted by means of diamond anvil cells in combination with optical spectroscopies and microscopy, synchrotron x-ray absorption spectroscopy and diffraction, as well as transmission electron microscopy. Our findings have the potential to stimulate further research into the high-pressure chemical reactivity of organometallics and open up new synthesis routes for the production of metal-based nanoparticles, which find a wide range of applications.
2023
Istituto di Chimica dei Composti OrganoMetallici - ICCOM -
Istituto Nazionale di Ottica - INO
High pressure engineering; High resolution transmission electron microscopy; Metal nanoparticles; Nanocomposites; Synthesis (chemical); X ray absorption spectroscopy; nickelocene
File in questo prodotto:
File Dimensione Formato  
prod_487757-doc_202744.pdf

embargo fino al 02/10/2024

Descrizione: “This article may be downloaded for personal use only. Any other use requires prior permission of the author and AIP Publishing. This article appeared in Samuele Fanetti, Sebastiano Romi, Enrico Berretti, Michael Hanfland, Emin Mijit, Frederico Alabarse, Philip Dalladay-Simpson, Federico Gorelli, Roberto Bini, Mario Santoro; High pressure decomposition of a sandwich compound. J. Chem. Phys. 7 October 2023; 159 (13): 134502 and may be found at https://doi.org/10.1063/5.0167748."
Tipologia: Versione Editoriale (PDF)
Licenza: Altro tipo di licenza
Dimensione 9.58 MB
Formato Adobe PDF
9.58 MB Adobe PDF   Visualizza/Apri   Richiedi una copia

I documenti in IRIS sono protetti da copyright e tutti i diritti sono riservati, salvo diversa indicazione.

Utilizza questo identificativo per citare o creare un link a questo documento: https://hdl.handle.net/20.500.14243/429252
Citazioni
  • ???jsp.display-item.citation.pmc??? ND
  • Scopus 0
  • ???jsp.display-item.citation.isi??? ND
social impact