SOME TRANSITION-METAL COMPLEXES DERIVED FROM SILYLATED 1,3-DIYNES

The complexes 2(mu-eta(2)-Me(3)SiC(2)C=CSiMe(3))(CO)(4)(cp)(2)], [Pt(e ta(2)-Me(3)SiC(2)C=CSiMe(3))(PPh(3))(2)] and mu(3)-eta(2)-Me(3)SiC(2)C =CSiMe(3))(mu-CO)(CO)(9)] have been prepared. Further reaction of the first with [Co-2(CO)(8)] gives O)6}(mu-eta(2):mu-eta(2)-Me(3)SiC(2)C(2 )SiMe(3))]. Desilylation of a(2)-Me(3)SiC(2)C=CSiMe(3))(mu-dppm)(n)(CO )(6-2n)] (n = 0 or 1, dppm = Ph(2)PCH(2)PPh(2)) gave [Co-2(mu-eta(2)-R C(2)C=CH)(mu-dppm)(n)(CO)(6-2n)] (n = 0, R = H; n = 1, R = SiMe(3) or H). The first dppm complex adds across the M-M bonds in [Re-2(CO)(8)(N CMe)(2)] and [Ru-3(CO)(12)] to give (2)-C(2)C(2)SiMe(3)[Co-2(mu-dppm)( CO)(4)]}(CO)(8)] and [Ru-3(mu-H){mu 2)-C(2)C(2)SiMe(3)[Co-2(mu-dppm)(C O)(4)]}(CO)(9)], respectively, while both dppm complexes react with [W Cl(CO)(3)(cp)] to give mu-eta(2)-RC(2)C=C[W(CO)(3)(cp)]}(mu-dppm)(CO)( 4)] (R = H or SiMe(3)). Auration of the HC(2)C(2)SiMe(3) complex with [AuCl(PPh(3))]-1,8-diazabicyclo [5.4.0]undec-7-ene gave a(2)-Me(3)SiC( 2)C=C[Au(PPh(3))]}(mu-dppm)(CO)(4)]. Addition of HC=CC=CSiMe(3) to [Ru -3(mu-dppm)(2)(CO)(8)] gave [Ru-3(mu-H)(mu(3)-eta(1) eta(2)-C-2-C=CSiM e(3))(mu-dppm)(2)(CO)(5)]. The complex [Os-3(CO10(NCMe)(2)] reacts wit h HC=CC=CSiMe(3) to give isomers of s-3(mu(3)-eta(2)-HC(2)C(2)SiMe(3)) (mu-CO)(CO)(9)]; the mixture reacts with [Co-2(CO)(8)] to give one iso mer of (2)-HC(2)C(2)SiMe(3)[Co-2(CO)(6)]}(mu-(CO)(CO)(9)] in which the Co-2 moiety bridges the C=CSiMe(3) portion of the diyne. The crystal structures of five of the complexes have been determined.