MONOMERIC (ACETYLACETONATO)COPPER(I) COMPLEXES OF ALKYNES AND 1,4-DIYNES

Monomeric (n(2)-Me(3)SiC=CSiMe(3))Cu(acac) (3) is formed by the reaction of dimeric [(eta(2)-Me(3)SiC=CSiMe(3))CuBr](2) (1) with two equivalents of Na(acac) (2). In a similar manner Me(2)Si(C=CSiMe(3))(2) (4) reacts with CuCl (5) and 2 to afford Me(2)Si[(eta(2)-C=CSiMe(3))Cu(acac)](2) (6). In compounds 3 and 6 an alkyne unit is eta(2)-coordinated to a monomeric Cu(acac) moiety with a copper atom in a planar environment. With the organometallic 1,4-diyne (eta(5)-C(5)H(4)SiMe(3))(2)Ti(C=CSiMe(3))(2) (7), compound [(eta(5)-C(5)H(4)SiMe(3))(2)Ti(C=CSiMe(3))(2)]Cu(acac) (8) is formed. In 8 both Me(3)SiC=C ligands of the 3 titanapenta-1,4-diyne fragment are eta(2)-coordinated to a monomeric Cu(acac) building block. The copper atom in 8 possesses a pseudo-tetrahedral environment (shown by X-ray analysis), built by the two Me(3)SiC=C ligands of the (eta(5)-C(5)H(4)SiMe(3))(2)Ti(C=CSiMe(3))(2) moiety and the two oxygen atoms of the acetylacetonato ligand. 8 is additionally formed by the reaction of 3 or 6 with 7, or by treatment of [(eta(5)-C(5)H(4)SiMe(3))(2)Ti(C=CSiMe(3))(2)]CuCl (9) with Na(acac) (2). The application of 3, 6, and 8 as precursors for the preparation of copper films in the CVD process of copper(I) is discussed.