(ETA(5)-CYCLOPENTADIENYL)BIS(THIOLATO)TITANIUM(IV) AND ZIRCONIUM(IV) - SYNTHESIS AND CRYSTAL-STRUCTURE OF CP(2)M(S(T)BU)(2)(M=TI,ZR) - USE OF CP(2)TI(S(T)BU)(2) AND CP(2)TI(SET)(2) AS SINGLE-SOURCE PRECURSORS FOR THE CHEMICAL-VAPOR-DEPOSITION OF TITANIUM SULFIDES

pentadienyl)bis(tertio-butanethiolato)titanium(IV) (1) and zirconium(I V) (2) were synthesized with a view to use them as single-source precu rsors for the preparation of thin films of titanium and zirconium sulf ides by the technique of chemical vapour deposition from metal-organic complexes (MOCVD). The crystal and molecular structures have been det ermined in order to compare them with those of homologous complexes of general formula (eta(5)-C5H5)(2)M(SR)(2). Both compounds are isostruc tural [monoclinic, sp. gr. C2/c; a = 16.450(6), b = 9.279(3), c = 12.7 07(4) Angstrom, beta = 108.27(4)degrees for 1; a = 16.604(8), b = 9.38 4(2), c = 12.884(6) Angstrom, beta = 107.86(2)degrees for 2]. The stru ctures are discussed according to the electron configuration of the ca tion and the bulkiness of the R substituant. CVD experiments were run using (1) or bis(eta 5-cyclopentadienyl)bis(ethanethiolato)titanium(IV ) (3) as single-source precursors, to grow titanium sulfide thin films . Films with S/Ti < 1 or S/Ti = 1, 1.3 and 1.5 have been obtained depe nding on the experimental conditions. CVD from (2) gave films with low to very low sulfur contents.