Exploiting sigma/pi coordination isomerism to prepare homologous organoalkali metal (Li, Na, K) monomers with identical ligand sets

Davidson, Matthew G. and Garcia-Vivo, Daniel and Kennedy, Alan R. and Mulvey, Robert E. and Robertson, Stuart D. (2011) Exploiting sigma/pi coordination isomerism to prepare homologous organoalkali metal (Li, Na, K) monomers with identical ligand sets. Chemistry - A European Journal, 17 (12). pp. 3364-3369. ISSN 0947-6539 (https://doi.org/10.1002/chem.201003493)

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Abstract

Tetraamine Me6TREN has been used as a scaffold support to provide coordinative saturation in the complexes PhCH2M center dot Me6TREN (M = Li, Na, K). The Li derivative displays a Li-C sigma interaction with a pyramidalized CH2 both in the solid state and in solution, and represents the first example of eta(4) coordination of Me6TREN to lithium. In the sodium derivative, the metal cation slips slightly towards the delocalized pi electrons whilst maintaining a partial sigma interaction with the CH2 group. For the potassium case, coordinative saturation successfully yields the first monomeric benzylpotassium complex, in which the anion binds to the metal cation exclusively through its delocalized pi system resulting in a planar CH2 group.

ORCID iDs

Davidson, Matthew G., Garcia-Vivo, Daniel, Kennedy, Alan R. ORCID logoORCID: https://orcid.org/0000-0003-3652-6015, Mulvey, Robert E. ORCID logoORCID: https://orcid.org/0000-0002-1015-2564 and Robertson, Stuart D. ORCID logoORCID: https://orcid.org/0000-0002-9330-8770;
  • Item type:Article
    ID code:33736
    Dates:
    Date
    Event
    14 March 2011
    Published
    21 February 2011
    Published Online
    Keywords:alkali metals, benzyl anion, coordination isomerism, monomer, polyamines, X-RAY, crystal structure, benzyl complexes, organometallic compounds, potassium, lithium, sodium, reagents, Physical and theoretical chemistry, Physical and Theoretical Chemistry
    Subjects:Science > Chemistry > Physical and theoretical chemistry
    Department:Faculty of Science > Pure and Applied Chemistry
    Depositing user: Pure Administrator
    Date deposited:18 Oct 2011 11:45
    Last modified:28 Sep 2022 14:00
    Related URLs:
    URI:https://strathprints.strath.ac.uk/id/eprint/33736
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