J. G. Hefner, P. Zizelman, L. Durfee
Jan 17, 1984
Citations
0
Influential Citations
9
Citations
Journal
Journal of Organometallic Chemistry
Abstract
Abstract The copper(I) trifluoromethanesulfonate π complexes of 1,8-cyclotetradecadiyne and 1,7-octadiyne have been synthesized. For a series of terminal alkyne (CuO 3 SCF 3 ) π complexes, vibrational spectra show weakening of both C ≡C and C sp -H bonds upon copper(I) coordination. NMR analysis shows less Cu(I) caused deshielding of C(1) than C(2) of the alkyne and increased C sp -H coupling. Copper(I) π coordination to terminal alkynes increases the rate of exchange of protium on C(1) for deuterium from CD 3 COOD. Copper enhances the rate of exchange by a factor of 1.2 x 10 5 with 1,7-octadiyne. The exchange is catalytic in copper(I) and is faster than the rate of copper alkynide formation in the absence of deuterium donor. Copper(I) catalyzes deuterium exchange for protium at C(1) between 1,7-octadiyne and 1-hexyne-1- d 1 .