Chemisches Institut der, Otto-von-Guericke-Universität, Universitätsplatz 2, 39106, Magdeburg, Germany.
Institut für Anorganische Chemie, Eberhard-Karls-Universität Tübingen, Auf der Morgenstelle 18, 7, 2076, Tübingen, Germany.
Angew Chem Int Ed Engl. 2017 Jun 12;56(25):7238-7241. doi: 10.1002/anie.201703362. Epub 2017 May 16.
The reactivity of Li[Sc(COT'') ] (1; COT''=1,4-bis(trimethylsilyl)cyclooctatetraenyl) towards CoCl is considerably different from that of related lanthanide triple-decker sandwich complexes. In addition to the expected triple-decker complex Sc (COT'') (2), the complex Sc {μ-BTHP}(COT'') (3) is formed, which comprises the novel BTHP ligand (BTHP =bis(3,5-bis(trimethylsilyl)-1,3a,6,6a-tetrahydropentalene-1-yl)diide or bis(2,7-bis(trimethylsilyl)bicyclo[3.3.0]octa-2,7-dien-4-yl)diide, C H (SiMe ) ). The formation of 3 is likely facilitated by the fact that scandium prefers η ,η coordination rather than highly symmetric η ,η coordination, and the η -coordinated COT'' ligand in 1 is activated owing to a loss of aromaticity. Acid hydrolysis of 3 leads to air-stable H BTHP (4).
Li[Sc(COT'')]（1；COT''=1,4-双（三甲基甲硅烷基）环辛四烯基）与 CoCl 的反应性与相关镧系元素三层夹心配合物有很大的不同。除了预期的三层夹心配合物 Sc（COT'）（2）外，还形成了配合物 Sc{μ-BTHP}（COT'）（3），其中包含了新颖的 BTHP 配体（BTHP=双（3,5-双（三甲基甲硅烷基）-1,3a,6,6a-四氢戊并[1,2-b]噻吩-1-基）二阴离子或双（2,7-双（三甲基甲硅烷基）降冰片二烯-4-基）二阴离子，C H（SiMe ））。由于钪更喜欢η,η配位而不是高度对称的η,η配位，并且 1 中η配位的 COT''配体由于失去芳香性而被活化，因此 3 的形成很可能得到了促进。3 的酸水解导致空气稳定的 HBTHP（4）。
