Scandium-Mediated Formation of a Bis(tetrahydropentalene)

Janek Rausch; Phil Liebing; Volker Lorenz; Liane Hilfert; Sabine Busse; Caecilia Maichle-Mössmer; Frank T Edelmann

doi:10.1002/anie.201703362

Scandium-Mediated Formation of a Bis(tetrahydropentalene)

Angew Chem Int Ed Engl. 2017 Jun 12;56(25):7238-7241. doi: 10.1002/anie.201703362. Epub 2017 May 16.

Authors

Janek Rausch¹, Phil Liebing¹, Volker Lorenz¹, Liane Hilfert¹, Sabine Busse¹, Caecilia Maichle-Mössmer², Frank T Edelmann¹

Affiliations

¹ Chemisches Institut der, Otto-von-Guericke-Universität, Universitätsplatz 2, 39106, Magdeburg, Germany.
² Institut für Anorganische Chemie, Eberhard-Karls-Universität Tübingen, Auf der Morgenstelle 18, 7, 2076, Tübingen, Germany.

PMID: 28510295
DOI: 10.1002/anie.201703362

Abstract

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 BTHP^2- ligand (BTHP^2- =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, C₁₆ H₁₀ (SiMe₃ )₄^2- ). 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 H₂ BTHP (4).

Keywords: X-ray diffraction; cyclooctatetraenes; lanthanides; sandwich complexes; scandium.

Publication types

Research Support, Non-U.S. Gov't