Solid-state NMR study of cyclohexane reorientation and inversion in (N-methyl-1,3-diaminopropane)cadmium(II) tetracyanonickelate(II)-cyclohexane (2/1) clathrate

• Published in: Journal of physical chemistry (1952) Vol. 94; no. 21; pp. 8098 - 8102
• Main Authors: Nishikiori, S, Ratcliffe, C. I, Ripmeester, J. A
• Format: Journal Article
• Language: English
• Published: Washington, DC American Chemical Society 01.10.1990
• Subjects: 400201 - Chemical & Physicochemical Properties; ALKANES; Analytical chemistry; CADMIUM COMPLEXES; CARBON 13; CARBON ISOTOPES; Chemistry; CLATHRATES; COMPLEXES; CYCLOALKANES; CYCLOHEXANE; EVEN-ODD NUCLEI; Exact sciences and technology; HIGH TEMPERATURE; HYDROCARBONS; INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; ISOTOPES; LIGHT NUCLEI; LOW TEMPERATURE; MAGNETIC RESONANCE; NICKEL COMPLEXES; NUCLEAR MAGNETIC RESONANCE; NUCLEI; ORGANIC COMPOUNDS; RESONANCE; Spectrometric and optical methods; STABLE ISOTOPES; TRANSITION ELEMENT COMPLEXES; Cadmium II Complexes; Solid state; Molecular motion; Temperature; Cyclohexane; Inversion; Transition metal Complexes; Nuclear magnetic resonance; Experimental study; Reorientation; Activation energy; Pressure
• ISSN: 0022-3654; 1541-5740
• DOI: 10.1021/j100384a022

The molecular motion of cyclohexane enclathrated in Cd(mtn)Ni(CN){sub 4}{center dot}{1/2}C{sub 6}H{sub 12} (mtn = CH{sub 3}NH(CH{sub 2}){sub 3}NH{sub 2}) was studied by CP/MAS {sup 13}C NMR and solid-state {sup 2}H NMR. At 77 K the chair form of cyclohexane is undergoing n-fold reorientation (n {ge} 3) about its 3-fold axis. This motion is retained to 397 K accompanied by inversion of the ring above ca. 239 K. The activation energy for the reorientation is estimated to be no more than 5.8 kJ/mol and for the inversion is found to be 44.7 {plus minus} 1.0 kJ/mol from a comparison of the experimental and simulated {sup 2}H NMR line shapes.