Pressure-Induced Reduction of Dicyanamide by Samarium(II) in a Coordination Polymer
Hannah B Wineinger1, Tyler W Hines1, Kacy N Mendoza1
1Department of Chemistry and Nuclear Science & Engineering Center, Colorado School of Mines, Golden, Colorado 80401, United States.
Abstract:
A samarium(II) coordination polymer, [Sm(2.2.2-cryptand)(dca)]I (dca- = dicyanamide), has been prepared from the reaction of SmI2 with tetrabutylammonium dicyanamide and 2.2.2-cryptand. The structure consists of [Sm(2.2.2-cryptand)]2+ cations bridged by dicyanamide to form corrugated 1D chains. Single crystals of this compound have been studied spectroscopically using UV-vis-NIR and Raman spectroscopy as a function of pressure to reveal a pressure-induced two-electron reduction of dicyanamide by Sm2+ to cyanide and cyanamide and Sm3+ between 5 and 8 GPa. High-pressure single-crystal diffraction studies reveal a phase change at 2.6 ± 0.1 GPa, where a polymorph exhibiting a smaller Sm2+···N≡C bond angle and shorter Sm2+···C distance was observed. These observations provide mechanistic insight into the reduction of dicyanamide into cyanide and cyanamide by pressurized samarium(II).
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