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A Thorough Characterization of the Tellurocyanate Anion

Journal Article · · Angewandte Chemie (International Edition)
 [1];  [2];  [1];  [3];  [3];  [3];  [1]
  1. Philipps University of Marburg (Germany)
  2. Karlsruhe Inst. of Technology (KIT), Eggenstein-Leopoldshafen (Germany)
  3. Pacific Northwest National Laboratory (PNNL), Richland, WA (United States)
+ Show Author Affiliations

Tellurocyanate, [TeCN]−, is the heaviest group 16 congener of the cyanate anion, [OCN]−. Due to the relative instability of the C─Te bond, tellurocyanate chemistry has seen only scarce attention. Here, we present the facile synthesis and thorough characterization of [K@crypt-222][TeCN]. The anion is essentially linear with interatomic distances C─N = 1.150(6)Å and C─Te = 2.051(4)Å, thus approximating a C≡N triple bond and for C─Te a bond order between 1 and 2. Fully 13C and 15N labeled [Te13C15N]− allowed for the extraction of chemical shifts and all possible coupling constants (13C = 77.8 ppm, 15N = 285.7 ppm, 125Te = −566 ppm, 1J13C-15N = 8 Hz, 1J13C-125Te = 748 Hz, 2J15N-125Te = 55 Hz), which were also determined independently by quantum chemical calculations. In the series [ChCN]− (Ch = O─Te), [TeCN]− shows the strongest spin-orbit coupling (SOC) induced heavy-atom effect on the light-atom shielding (SO-HALA-effect). In contrast, 15N shifts are also well described without considering relativistic effects and/or SOC. Negative-ion photoelectron spectroscopy was used to extract the electron affinity (EA = 3.034 eV) and spin-orbit splitting (3807 cm−1) of [TeCN]•. These values continue the trends of falling EA and rising SOC in the series [ChCN]•.

Research Organization:
Pacific Northwest National Laboratory (PNNL), Richland, WA (United States)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division (CSGB)
Grant/Contract Number:
AC05-76RL01830
OSTI ID:
2998795
Report Number(s):
PNNL-SA--211739
Journal Information:
Angewandte Chemie (International Edition), Journal Name: Angewandte Chemie (International Edition) Journal Issue: 31 Vol. 64; ISSN 1521-3773; ISSN 1433-7851
Publisher:
WileyCopyright Statement
Country of Publication:
United States
Language:
English

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Related Subjects

Bonding analysis
Cyanates
DFT
Negative ion photoelectron spectroscopy
Nuclear magnetic resonance