Synthesis, characterization and reactivity of a series of alkaline earth and rare earth iminophosphoranomethanide complexes

Abstract There is a great demand from the synthetic community for readily accessible organometallic alkaline earth and rare earth compounds that can be used as synthons for the preparation of new complexes and materials. Here we report the use of the methanide ligand {CH(SiMe3)P(Ph)2 = NSiMe3}– (NPC...

Full description

Saved in:
Bibliographic Details
Main Authors: Matthew P. Stevens, Yu Liu, Elias Alexopoulos, Shifaa S. A. Xec Daudo, Rebecca R. Hawker, Adam Khan, Luis Lezama, Daniel Reta, Fabrizio Ortu
Format: Article
Language:English
Published: Nature Portfolio 2025-06-01
Series:Communications Chemistry
Online Access:https://doi.org/10.1038/s42004-025-01572-5
Tags: Add Tag
No Tags, Be the first to tag this record!
_version_ 1849470098919653376
author Matthew P. Stevens
Yu Liu
Elias Alexopoulos
Shifaa S. A. Xec Daudo
Rebecca R. Hawker
Adam Khan
Luis Lezama
Daniel Reta
Fabrizio Ortu
author_facet Matthew P. Stevens
Yu Liu
Elias Alexopoulos
Shifaa S. A. Xec Daudo
Rebecca R. Hawker
Adam Khan
Luis Lezama
Daniel Reta
Fabrizio Ortu
author_sort Matthew P. Stevens
collection DOAJ
description Abstract There is a great demand from the synthetic community for readily accessible organometallic alkaline earth and rare earth compounds that can be used as synthons for the preparation of new complexes and materials. Here we report the use of the methanide ligand {CH(SiMe3)P(Ph)2 = NSiMe3}– (NPC-H) in the stabilization of alkaline earth and rare earth organometallics and their potential use as synthetic precursors. Bis- and tris-methanide complexes were obtained following two methods: (1) deprotonation of the proligand with organometallic precursors; (2) salt elimination reactivity between potassium methanide and metal iodides. All compounds were characterised by multinuclear nuclear magnetic resonance, infra-red spectroscopy, elemental analysis, ultraviolet-visible spectroscopy and single crystal X-ray diffraction. Additionally, selected rare earth methanides were tested as synthetic precursors for the preparation of solvent-free rare earth complexes. Finally, the electronic structures of open-shell divalent rare earth methanides were probed using electron paramagnetic resonance, magnetometry studies and ab initio calculations.
format Article
id doaj-art-cf4ca778435740a48d18327d0ec1ffdb
institution Kabale University
issn 2399-3669
language English
publishDate 2025-06-01
publisher Nature Portfolio
record_format Article
series Communications Chemistry
spelling doaj-art-cf4ca778435740a48d18327d0ec1ffdb2025-08-20T03:25:15ZengNature PortfolioCommunications Chemistry2399-36692025-06-018111610.1038/s42004-025-01572-5Synthesis, characterization and reactivity of a series of alkaline earth and rare earth iminophosphoranomethanide complexesMatthew P. Stevens0Yu Liu1Elias Alexopoulos2Shifaa S. A. Xec Daudo3Rebecca R. Hawker4Adam Khan5Luis Lezama6Daniel Reta7Fabrizio Ortu8School of Chemistry, University of Leicester, University RoadSchool of Chemistry, University of Leicester, University RoadSchool of Chemistry, University of Leicester, University RoadSchool of Chemistry, University of Leicester, University RoadSchool of Chemistry, University of Leicester, University RoadSchool of Chemistry, University of Leicester, University RoadDepartamento de Química Orgánica e Inorgánica, Facultad de Ciencia y Tecnología, Universidad del País Vasco, B° Sarriena s/nFaculty of Chemistry, The University of the Basque Country UPV/EHUSchool of Chemistry, University of Leicester, University RoadAbstract There is a great demand from the synthetic community for readily accessible organometallic alkaline earth and rare earth compounds that can be used as synthons for the preparation of new complexes and materials. Here we report the use of the methanide ligand {CH(SiMe3)P(Ph)2 = NSiMe3}– (NPC-H) in the stabilization of alkaline earth and rare earth organometallics and their potential use as synthetic precursors. Bis- and tris-methanide complexes were obtained following two methods: (1) deprotonation of the proligand with organometallic precursors; (2) salt elimination reactivity between potassium methanide and metal iodides. All compounds were characterised by multinuclear nuclear magnetic resonance, infra-red spectroscopy, elemental analysis, ultraviolet-visible spectroscopy and single crystal X-ray diffraction. Additionally, selected rare earth methanides were tested as synthetic precursors for the preparation of solvent-free rare earth complexes. Finally, the electronic structures of open-shell divalent rare earth methanides were probed using electron paramagnetic resonance, magnetometry studies and ab initio calculations.https://doi.org/10.1038/s42004-025-01572-5
spellingShingle Matthew P. Stevens
Yu Liu
Elias Alexopoulos
Shifaa S. A. Xec Daudo
Rebecca R. Hawker
Adam Khan
Luis Lezama
Daniel Reta
Fabrizio Ortu
Synthesis, characterization and reactivity of a series of alkaline earth and rare earth iminophosphoranomethanide complexes
Communications Chemistry
title Synthesis, characterization and reactivity of a series of alkaline earth and rare earth iminophosphoranomethanide complexes
title_full Synthesis, characterization and reactivity of a series of alkaline earth and rare earth iminophosphoranomethanide complexes
title_fullStr Synthesis, characterization and reactivity of a series of alkaline earth and rare earth iminophosphoranomethanide complexes
title_full_unstemmed Synthesis, characterization and reactivity of a series of alkaline earth and rare earth iminophosphoranomethanide complexes
title_short Synthesis, characterization and reactivity of a series of alkaline earth and rare earth iminophosphoranomethanide complexes
title_sort synthesis characterization and reactivity of a series of alkaline earth and rare earth iminophosphoranomethanide complexes
url https://doi.org/10.1038/s42004-025-01572-5
work_keys_str_mv AT matthewpstevens synthesischaracterizationandreactivityofaseriesofalkalineearthandrareearthiminophosphoranomethanidecomplexes
AT yuliu synthesischaracterizationandreactivityofaseriesofalkalineearthandrareearthiminophosphoranomethanidecomplexes
AT eliasalexopoulos synthesischaracterizationandreactivityofaseriesofalkalineearthandrareearthiminophosphoranomethanidecomplexes
AT shifaasaxecdaudo synthesischaracterizationandreactivityofaseriesofalkalineearthandrareearthiminophosphoranomethanidecomplexes
AT rebeccarhawker synthesischaracterizationandreactivityofaseriesofalkalineearthandrareearthiminophosphoranomethanidecomplexes
AT adamkhan synthesischaracterizationandreactivityofaseriesofalkalineearthandrareearthiminophosphoranomethanidecomplexes
AT luislezama synthesischaracterizationandreactivityofaseriesofalkalineearthandrareearthiminophosphoranomethanidecomplexes
AT danielreta synthesischaracterizationandreactivityofaseriesofalkalineearthandrareearthiminophosphoranomethanidecomplexes
AT fabrizioortu synthesischaracterizationandreactivityofaseriesofalkalineearthandrareearthiminophosphoranomethanidecomplexes