SYNTHETIC AND STRUCTURAL STUDIES ON MONOMERIC OLEFIN AND ISOCYANIDE COMPLEXES OF COPPER(I) - (DIETHYLENETRIAMINE)(1-HEXENE)COPPER(I) TETRAPHENYLBORATE AND (N,N,N',N'-TETRAMETHYLETHYLENEDIAMINE)BIS(CYCLOHEXYL ISOCYANIDE)COPPER(I) TETRAPHENYLBORATE

The reaction of a suspension of Cul in methanol containing diethylenetriamine (dien) with 1-hexene gives the olefin complex [Cu(dien)(l-hexene)]+, which was isolated as a tetraphenylborate derivative. In the complex cation, dien is coordinated through the three nitrogen atoms to the metal, while the C=C bond of the 1-hexene molecule completes the pseudotetrahedral coordination around copper(I). The reaction of a suspension of Cul in methanol containing ethylenediamine (en) or N,N,N',N'-tetramethylethylenediamine (tmen) with carbon monoxide followed by the addition of CNC6Hn produces [Cu(en)(CNC6Hn)2]+ [cCn (Nujol) 2143 and 2177 cm-1] or [Cu (tmen) (CNC6H12)2]+ [vCN (Nujol) 2160 and 2180 cm-1], respectively. The tetrahedral structure of the cationic complex in which copper (I) coordinates a chelating tmen and two C-bonded isocyano groups, was confirmed by an X-ray analysis. Both the Cu-C-N and C-N-R moieties are practically linear with Cu-C and C-N bond lengths of 1.899 (8) and 1.895 (7) υ and C-N bond lengths of 1.15 (1) and 1.13 (1) υ. Crystallographic details for [Cu(dien)(C6H12)](BPh4): space group P2Jc (monoclinic), a=15.835 (2) υ, b=20.346 (3) υ, c=20.219 (3) υ, β=96.21 (2)°, Z=8. The final R factor was 11.5% for 4297 observed reflections. Crystallographic details for [Cu(tmen)(CNC6Hn)2](BPh4): space group P21/n (monoclinic), a=15.626 (2) υ, b=14.753 (3) υ, c=18.024 (4) υ, β=97.47 (2)°, Z=4. The final R factor was 6.9% for 3860 observed reflections. © 1979, American Chemical Society. All rights reserved.