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sup 113 Cd shielding tensors of cadmium compounds. 6. Single-crystal NMR study of the CdCl sub 2 times 18-crown-6 complex

Journal Article · · Inorganic Chemistry; (USA)
DOI:https://doi.org/10.1021/ic00328a042· OSTI ID:6944978
;  [1];  [2]
  1. Univ. of South Carolina, Columbia (USA)
  2. Univ. of Aarhus (Denmark)
The {sup 113}Cd chemical shielding tensor and its orientation in the molecular frame have been determined for CdCl{sub 2} {times} 18-crown-6 via a solid-state single-crystal NMR experiment. The shielding tensor elements are found to be {sigma}{sub 33} = {minus}700 ppM, {sigma}{sub 2}2 = 385 ppM, and {sigma}{sub 11} = 414 ppM. The anisotropy and asymmetry parameters are determined to be {Delta}{sigma} = {minus} 1,100 ppM and {eta} = 0.04, respectively. The unique shielding tensor element, {sigma}{sub 22}, lies 2.4{degree} from the 3-fold rotation axis of the crown ligand and was also found to be the most shielded tensor element {sigma}{sub 33}. The structural feature that determines the orientation of {sigma}{sub 33} is found to be the anomalously long Cd-O bond lengths, i.e. 2.75 {angstrom}. The unusually large magnitude of the most shielded tensor element is analyzed in terms of the special geometry and corresponding shielding trend established for a series of cadmium complexes with similar porphyrin and crown ligands. 15 refs., 2 figs., 3 tabs.
OSTI ID:
6944978
Journal Information:
Inorganic Chemistry; (USA), Journal Name: Inorganic Chemistry; (USA) Vol. 29:3; ISSN 0020-1669; ISSN INOCA
Country of Publication:
United States
Language:
English