SYNTHESIS AND REACTION BEHAVIOR OF THE NOVEL MONO(SIGMA-ALKYNYL)TITANOCENE CHLORIDE ETA(5)-C(5)H(2)SIME(3))SIME(2)]TI-2(CL)(CCSIME(3))

The reaction of [(eta(5)-C(5)H(2)SiMe(3))SiMe(2)]2TiCl2 (1) with 1 equ iv of LiCCSiMe(3) (2) yields the novel mono(sigma-alkynyl)titanocene c hloride [(eta(5)-C(5)H(2)SiMe(3))SiMe(2)]Ti-2(Cl)(CCSiMe3) (3). 3 can be used as an organometallic chelating ligand for the stabilization of monomeric [CuX] entities [X = Cl, Br, O(2)CMe], yielding (eta(5)-C(5) H(2)SiMe(3))SiMe(2)]Ti-2(Cl)(CCSiMe3)} CuX [5a, X = Cl; 5b, X = Br; 5c , X = O(2)CMe]. The X-ray structure analyses of 3 and 5a are reported. Crystals of 3 are orthorhombic, space group Pna2(1), with a = 20.22(2 ) Angstrom, b = 10.949(8) Angstrom, c = 29.53(3) Angstrom, V = 6537(9) Angstrom(3),and Z = 8; crystals of 5a are triclinic, space group P ($ ) over bar 1 with a = 11.195(3) Angstrom, b = 11.502(3) Angstrom, c = 14.788(4) Angstrom, alpha = 96.27(2)degrees, B = 110.62(2)degrees, gam ma = 100.90(2)degrees, V = 1717.7(8) Angstrom(3), and Z = 2.