Solid-state and solution 13C NMR data for the monomers and dimers of 3- and 4-substituted nitrosobenzenes, and the crystal structure of E-(4-CIC6H4NO)2 are reported.
The title complex is asymmetric in the crystal due to the spatial orientation of the NCS function. The space group has been determined to be P21 with a = 9.496(3), b = 8.736(3), c = 9.676(3) Å, β = 117.859(5)°, and Z = 2. The solid state 13C NMR spectrum is consistent with the lack of symmetry in the crystal and there is little evidence for large amplitude motion in the macrocycle as determined from the dipolar dephased spectrum.Key words: macrocyclic crown ether, lithium complex.
Abstract
In summary, the solid-state C-13 NMR technique has proven to be a significant method for the detection of crosslinks and other structural modifications in sulfur-vulcanized NR systems. The use of sulfur as a crosslinking agent by itself generates a considerable amount of main-chain structural modifications. Cyclic sulfide structures and cis-to-trans chain isomerization are detected in addition to polysulfidic crosslinks which are found attached to different carbons of the NR repeat unit. The phenomenon of reversion has also been detected in this study. The nature of the spectral broadening in the NMR spectra of the highly cured vulcanizates has two origins. The broadening arises from lack of molecular motion in the system and from an increase in chemical shift dispersion due to the new structures formed with crosslinking.
Structural Investigations of C-Nitrosobenzenes. Part 3.1 Solid-state and Solution 13C NMR Studies, and Crystal Structure of E-(4-CIC6H4NO)2