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Verfasst von:Eberle, Lukas [VerfasserIn]   i
 Lindenthal, Sebastian [VerfasserIn]   i
 Ballmann, Joachim [VerfasserIn]   i
Titel:To split or not to split
Titelzusatz:(AsCCAs)-coordinated Mo, W, and Re complexes and their reactivity toward molecular dinitrogen
Verf.angabe:Lukas Eberle, Sebastian Lindenthal, and Joachim Ballmann
E-Jahr:2024
Jahr:February 15, 2024
Umfang:10 S.
Illustrationen:Illustrationen
Fussnoten:Im Zusatz zum Titel steht AsCCAs in eckiger Klammer ; Gesehen am 15.05.2024
Titel Quelle:Enthalten in: Inorganic chemistry
Ort Quelle:Washington, DC : American Chemical Society, 1962
Jahr Quelle:2024
Band/Heft Quelle:63(2024), 8 vom: Feb., Seite 3682-3691
ISSN Quelle:1520-510X
Abstract:Molybdenum, tungsten, and rhenium halides bearing a 2,2′-(iPr2As)2-substituted diphenylacetylene ([AsCCAs], 1-As) were prepared and reduced under an atmosphere of dinitrogen in order to activate the latter substrate. In the case of molybdenum, a diiodo (2-As) and a triiodo molybdenum precursor (5) were equally suited for reductive N2 splitting, which led to the isolation of [AsCCAs]Mo≡N(I) (3-As) in each case. For tungsten, [AsCCAs]WCl3 (6) was reduced under N2 to afford {[AsCCAs]WCl2}2(N2) (7), which is best described as a dinuclear π8δ4-configured μ-(η1: η1)-N2-bridged dimer. Attempts to reductively cleave the N2 unit in 7 did not lead to the expected tungsten nitride (8), which had to be prepared independently via the treatment of 7 with sodium azide. To arrive at a π10δ4-configured N2-bridged dimer in a tetragonally distorted ligand environment, [AsCCAs]ReCl3 (9) was reduced in the presence of N2. As expected, a μ-(η1: η1)-N2-bridged dirhenium species, namely, {[AsCCAs]ReCl2}2(N2) (10), was formed, but found to very quickly decompose (presumably via loss of N2), not only under reduced pressure, but also upon irradiation or heating. Hence, an alternative synthetic route to the originally envisioned nitride, [AsCCAs]Re≡N(Cl)2 (11), was developed. While all the aforementioned nitrides (3-As, 8, and 11) were found to be fairly robust, significantly different stabilities were noticed for {[AsCCAs]MCl2}2(N2) (7 for M = W, 10 for M = Re), which is ascribed to the electronically different MN2M cores (π8δ4 for 7 vs π10δ4 for 10) in these μ-(η1: η1)-N2-bridged dimers.
DOI:doi:10.1021/acs.inorgchem.3c03244
URL:Bitte beachten Sie: Dies ist ein Bibliographieeintrag. Ein Volltextzugriff für Mitglieder der Universität besteht hier nur, falls für die entsprechende Zeitschrift/den entsprechenden Sammelband ein Abonnement besteht oder es sich um einen OpenAccess-Titel handelt.

Volltext: https://doi.org/10.1021/acs.inorgchem.3c03244
 DOI: https://doi.org/10.1021/acs.inorgchem.3c03244
Datenträger:Online-Ressource
Sprache:eng
K10plus-PPN:1888695064
Verknüpfungen:→ Zeitschrift

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