Synthesis of Alkynechalcogenolato Complexes of Titanocene(IV) and Samarocene(III) and Formation of a Ti(2)Ni Trinuclear Cluster [Cp(2)Ti(&mgr;-SC&tbd1;CPh)(2)](2)Ni.
Reactions between (C(5)H(4)R')(2)TiCl(2) and 2 equiv of LiEC&tbd1;CR generated a series of alkynethiolato and alkyneselenolato complexes of titanocene(IV), (C(5)H(4)R')(2)Ti(EC&tbd1;CR)(2) in high yields (1, R = Ph, R' = H, E = S; 2, R = p-C(6)H(4)CH(3), R' = H, E = S; 3, R = (t)Bu, R' = H, E = S; 4, R = Ph, R' = Me, E = S; 5, R = Ph, R' = H, E = Se). Complex 1 reacted with (1)/(2) equiv of Ni(cod)(2) to give a linear Ti(2)Ni trimetallic complex, [Cp(2)Ti(&mgr;-SC&tbd1;CPh)(2)](2)Ni (6), in which the Ni atom links two Cp(2)Ti(SC&tbd1;CPh)(2) units through interactions with thiolate sulfur bridges. Treatment of Cp(2)Sm(&mgr;-Cl)(2)Li(OEt(2))(2) with 2 equiv of LiSC&tbd1;CPh and TMEDA resulted in [Li(tmeda)(2)][Cp(2)Sm(SC&tbd1;CPh)(2)] (7). The structures of complexes 4, 5, 6, and 7 were determined by X-ray diffraction analysis.
Sugiyama
Hiroyasu
H
Research Center for Materials Science, and Department of Chemistry, Graduate School of Science, Nagoya University, Furo-cho, Chikusa-ku, Nagoya 464-8602, Japan.
Hayashi
Yuji
Y
Kawaguchi
Hiroyuki
H
Tatsumi
Kazuyuki
K