Individual polyynes in the series H (C C) n (n= 4–10, 12) have been prepared in solution by sequences involving Cu-catalysed oxidative couplings (Hay technique) of silyl-protected terminal alkynes, partial cleavage (desilylation) of the products by alkali, recoupling and complete desilylation. Thus using the conditions established in a model coupling, Et3SiC CH (I)→ Et3Si (C SiEt3 (II), coupling of the silyidiyne Et3Si (C C) 2H (II) gives Et3Si (C ...