Structural characterization of the 1-metallo-2- t -butyl-1,2-dihydropyridyl rubidium and caesium complexes
MacDonald, Peter A. and Banerjee, Sumanta and Kennedy, Alan R. and Mulvey, Robert E. and Robertson, Stuart D. (2023) Structural characterization of the 1-metallo-2- t -butyl-1,2-dihydropyridyl rubidium and caesium complexes. Polyhedron, 234. 116302. ISSN 0277-5387 (https://doi.org/10.1016/j.poly.2023.116302)
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Abstract
With recent reports of alkali metal amides used in homogeneous catalytic chemistry where the reactivity down group one is dependent on the metal identity, esoteric rubidium and caesium amides are finding new admirers amongst chemists who usually study lithium, sodium, and potassium utility amides. Here, as a forerunner to their exploitation in catalysis, we report the X-ray crystallographic and NMR solution structures of the 1-metallo-2-t-butyl-1,2-dihydropyridyl (DHP) complexes of rubidium and caesium, thereby completing the homologous alkali metal series. Crystallized as monosolvated {[Rb(tBuDHP)·THF] 2} ∞ and hemisolvated {[Cs(tBuDHP)] 2·THF} ∞, both form spectacular supramolecular structures. While each shares a plethora of metallo-π-contacts with the DHP anion, their subunits differ. The former dimerizes in a ‘slipped’ fashion via interactions between the symmetrically-equivalent Rb centres and the π-system of the adjacent DHP ring, but the latter has distinct Cs centres within its dinuclear subunit, with one Cs engaging in σ-bonding to two tBuDHP anions, whereas the other Cs binds in a more side-on fashion to the π-system of the ring.
ORCID iDs
MacDonald, Peter A., Banerjee, Sumanta, Kennedy, Alan R. ORCID: https://orcid.org/0000-0003-3652-6015, Mulvey, Robert E. ORCID: https://orcid.org/0000-0002-1015-2564 and Robertson, Stuart D. ORCID: https://orcid.org/0000-0002-9330-8770;-
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Item type: Article ID code: 83795 Dates: DateEvent1 April 2023Published20 January 2023Published Online17 January 2023AcceptedSubjects: Science > Chemistry > Physical and theoretical chemistry Department: Faculty of Science > Pure and Applied Chemistry Depositing user: Pure Administrator Date deposited: 23 Jan 2023 12:29 Last modified: 30 Nov 2024 14:22 Related URLs: URI: https://strathprints.strath.ac.uk/id/eprint/83795