二茂钛（IV）和二茂钐（III）的炔基硫属醇盐配合物的合成以及Ti(2)Ni三核簇[Cp(2)Ti(μ-SC≡CPh)(2)](2)Ni的形成。

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.

作者信息

Sugiyama Hiroyasu, Hayashi Yuji, Kawaguchi Hiroyuki, Tatsumi Kazuyuki

机构信息

Research Center for Materials Science, and Department of Chemistry, Graduate School of Science, Nagoya University, Furo-cho, Chikusa-ku, Nagoya 464-8602, Japan.

出版信息

Inorg Chem. 1998 Dec 28;37(26):6773-6779. doi: 10.1021/ic980901x.

DOI:10.1021/ic980901x

PMID:11670812

Abstract

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)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.

摘要

（C(5)H(4)R'）(2)TiCl(2) 与 2 当量的 LiEC≡CR 反应，高产率地生成了一系列二茂钛（IV）的炔硫醇盐和炔硒醇盐配合物（C(5)H(4)R'）(2)Ti(EC≡CR)(2)（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）。配合物 1 与（1）/（2）当量的 Ni(cod)(2) 反应，得到线性的 Ti(2)Ni 三金属配合物 Cp(2)Ti(μ-SC≡CPh)(2)Ni （6），其中 Ni 原子通过与硫醇盐硫桥的相互作用连接两个 Cp(2)Ti(SC≡CPh)(2) 单元。用 2 当量的 LiSC≡CPh 和 TMEDA 处理 Cp(2)Sm(μ-Cl)(2)Li(OEt(2))(2)，得到 [Li(tmeda)(2)][Cp(2)Sm(SC≡CPh)(2)] （7）。通过 X 射线衍射分析确定了配合物 4、5、6 和 7 的结构。