Jump to main content
Jump to site search


Scandium alkyl and hydride complexes supported by a pentadentate diborate ligand: reactions with CO2 and N2O

Author affiliations

Abstract

Alkyl and hydrido scandium complexes of the dianionic pentadentate ligand B2Pz4Py are reported. The key starting material (B2Pz4Py)ScCl is readily prepared and alkylated with organolithium reagents RLi (R = CH3, CH2SiMe3, CH2SiMe2Ph, CH2CH2CH3 and CH2CHMe2) to form alkyl derivatives in 61–93% yields. These compounds are very thermally stable and do not undergo sigma bond metathesis reactions with dihydrogen. The hydrido complex was prepared from (B2Pz4Py)ScCl and NaHBEt3 in 80% yield and was found to be more stable by 28 kcal mol−1 as a dimer, rather than a monomeric hydrido complex. However, the monomer is accessible through dissociation of the dimer at 80 °C. All of the compounds (B2Pz4Py)ScR react with water to form the bridging oxo dimer (B2Pz4Py)ScOSc(B2Pz4Py). The reactivity of the hydrido and methyl complexes towards carbon dioxide was explored; heating to 80 °C results in the formation of κ2 formato and acetate complexes, respectively. The mechanisms were studied via density functional theory and distinct transition states for insertion of CO2 into the Sc–R (R = H, CH3) were found, with the insertion into Sc–CH3 being more enthalpically difficult (by 18 kcal mol−1) than insertion into Sc–H. The slow rate of reaction between [(B2Pz4Py)ScH]2 and CO2 is attributed to the barrier associated with dimer dissociation. In both insertion reactions, the kinetic products are κ1 formato or acetate complexes that are only slightly less stable than the observed κ2 derivatives. The κ1 compounds can therefore be trapped by treating the κ2 isomers with tris-pentafluorophenyl borane.

Graphical abstract: Scandium alkyl and hydride complexes supported by a pentadentate diborate ligand: reactions with CO2 and N2O

Back to tab navigation

Supplementary files

Publication details

The article was received on 13 Aug 2018, accepted on 10 Sep 2018 and first published on 10 Sep 2018


Article type: Paper
DOI: 10.1039/C8DT03313G
Citation: Dalton Trans., 2018, Advance Article
  •   Request permissions

    Scandium alkyl and hydride complexes supported by a pentadentate diborate ligand: reactions with CO2 and N2O

    D. W. Beh, W. E. Piers, I. del Rosal, L. Maron, B. S. Gelfand, C. Gendy and J. Lin, Dalton Trans., 2018, Advance Article , DOI: 10.1039/C8DT03313G

Search articles by author

Spotlight

Advertisements