4.4 Article

[Ag7(H){S2CC(CN)2}6]6-: An Anionic Heptanuclear Silver Hydride Cluster Compound Stabilized by Dithiolate Ligands

Journal

JOURNAL OF CLUSTER SCIENCE
Volume 30, Issue 5, Pages 1185-1193

Publisher

SPRINGER/PLENUM PUBLISHERS
DOI: 10.1007/s10876-019-01538-3

Keywords

Luminescence; Silver(I) clusters; Hydride; S-donor; Ag-109 NMR

Funding

  1. Ministry of Science and Technology of Taiwan [MOST 106-2113-M-259-010]
  2. National Natural Science Foundation of China [21601097]
  3. National First-rate Discipline Construction Project of Ningxia (Chemical Engineering Technology) [NXYLXK2017A04]

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In our attempts to identify probable intermediates in the preparation of anionic silver hydride cluster [Ag-8(H){S2CC(CN)(2)}(6)](5-) under the condition of excess NaBH4, we isolated and analyzed a new cluster compound, namely, [Bu4N](6)[Ag-7(H){S2CC(CN)(2)}(6)]. We report here the synthesis, crystal structure, characterizations by various spectroscopic (UV-Vis, IR, multinuclear NMR, elemental analyses) techniques and the luminescent properties of this cluster. Its X-ray crystal structure reveals that the cluster contains a distorted; tricapped tetrahedral silver core enclosed an interstitial hydride anion and is surrounded by six 1,1-dicyanoethylene-2,2-dithiolate ([S2CC(CN)(2)](2-), i-MNT) ligands. The presence of hydride inside the heptanuclear silver cluster is unequivocally certified by both H-1 and Ag-109 NMR spectroscopies. The title compound represents the first atomic precisely anionic Ag-7-H skeleton with a non-disordered, tricapped tetrahedral silver framework.

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