13C13C coupling constants in diacetylene (1,3‐butadiyne) and its bis(triethylsilyl) derivative

Abstract

AbstractCompletely 13C‐labelled diacetylene and its bis(triethylsilyl) derivative have been synthesized and all the possible spin–spin couplings between the acetylenic carbon nuclei have been determined from their Fourier transform 13C NMR spectra. J(CC) values in diacetylene have been also computed by means of the finite perturbation INDO method. Carbon–proton coupling constants in diacetylene have been determined from the spectrum at natural abundance. It has been established that J(CC) values across the triple bond in diacetylene and bis(triethylsilyl)diacetylene are greater than in acetylene and triethylsilylacetylene, respectively. The increase is interpreted in terms of σ‐ and π‐electronic changes which occur with the coupling of two isolated triple bonds into a dimer‐like system. All CC coupling constants are greater in diacetylene than in bis(triethylsilyl)diacetylene, which indicates that strong (p→d)π interaction takes place in the latter compound.