Spectra edited by relative signs of homonuclear couplings of low abundance nuclei

Abstract

The proposed homonuclear coupling sign edited (HCSE) experiment can detect signed homonuclear couplings between low abundant nuclei like (13)C, (29)Si and (15)N in linear spin systems, that is, in systems where two nuclei are coupled by the measured coupling, and one of them is coupled by a second coupling to a nucleus of different kind. The third nucleus is usually high abundant hydrogen. Two spectra are measured during the HCSE experiment. Their weighed sum and difference yield two other spectra, one containing peaks coupled only by positive measured couplings and the other having peaks coupled by negative measured couplings. The usual E.COSY-type experiment requires all three couplings in the three spin system (triangular spin system) and not only two couplings as the HCSE experiment. The experiment was successfully tested on known carbon-carbon and silicon-silicon two bond couplings. A set of six simple siloxanes with |(2) J(Si-O-Si)| couplings ranging from 0.5 to 9.0 Hz was measured for the first time, and all the couplings were found to be positive.