A Simple Route to Calcium and Strontium Hydride Clusters. (23rd August 2017)

• Record Type: Journal Article
• Authors: Maitland, Brant; Wiesinger, Michael; Langer, Jens; Ballmann, Gerd; Pahl, Jürgen; Elsen, Holger; Färber, Christian; Harder, Sjoerd
• Is Part Of: Angewandte Chemie. Volume 129:Number 39(2017)
• Page Start: 12042
• Page End: 12046
• Publication Date: 2017-08-23
• Subjects: Calcium -- Erdalkalimetalle -- Hydride -- Selbstorganisation -- Strontium; Chemistry -- Periodicals; 540
• DOI: 10.1002/ange.201706786
• Languages: English
• ISSNs: 0044-8249

Abstract

Abstract: The first strontium hydride complex has been obtained by simply treating Sr[N(SiMe3 )2 ]2 with PhSiH3 in the presence of PMDTA. The Sr complex Sr6 H9 [N(SiMe3 )2 ]3 ⋅(PMDTA)3 crystallizes as an "inverse cryptand": an interstitial H − is surrounded by a Sr6 H8 4+ cage decorated with amide and PMDTA ligands. The analogous Ca complex could also be obtained and both retain their solid‐state structures in solution: 1 H NMR spectra in C6 D6 show two doublets and one nonet (4:4:1). Up to 90 °C, no coalescence is observed. The Ca cluster was investigated by DFT calculations and shows atypically low charges on Ca (+1.14) and H (−0.59) which signifies an unexpectedly low ionicity. AIM analysis shows hydride⋅⋅⋅hydride bond paths with considerable electron densities in the bond critical point. The clusters thermally decompose into larger, undefined, metal hydride aggregates.