4 years ago

Scandium-Mediated Formation of a Bis(tetrahydropentalene)

Scandium-Mediated Formation of a Bis(tetrahydropentalene)
Phil Liebing, Sabine Busse, Caecilia Maichle-Mössmer, Liane Hilfert, Volker Lorenz, Frank T. Edelmann, Janek Rausch
The reactivity of Li[Sc(COT′′)2] (1; COT′′=1,4-bis(trimethylsilyl)cyclooctatetraenyl) towards CoCl2 is considerably different from that of related lanthanide triple-decker sandwich complexes. In addition to the expected triple-decker complex Sc2(COT′′)3 (2), the complex Sc2{μ-BTHP}(COT′′)2 (3) is formed, which comprises the novel BTHP2− ligand (BTHP2−=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, C16H10(SiMe3)42−). The formation of 3 is likely facilitated by the fact that scandium prefers η8,η3 coordination rather than highly symmetric η8,η8 coordination, and the η3-coordinated COT′′ ligand in 1 is activated owing to a loss of aromaticity. Acid hydrolysis of 3 leads to air-stable H2BTHP (4). Unusual coordination: A unique bis(tetrahydropentalene) has been constructed via a series of structurally remarkable scandium complexes. Its formation is likely promoted by the fact that scandium prefers η8,η3 over η8,η8 coordination.

Publisher URL: http://onlinelibrary.wiley.com/resolve/doi

DOI: 10.1002/anie.201703362

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