Bis(η5-cyclopentadienyl)[μ-(4b,5,5a-η3:9b,10,10a-η3)-2,3,7,8-tetrakis(trimethylsilyl)benzo[3,4]cyclobuta[1,2-b]biphenylene]-syn-dicobalt (Co–Co), a Dinuclear π-Complex of the Linear [3]Phenylene Framework

Robin Padilla; K. Peter C. Vollhardt; Kendall N. Houk; Jonathan J. Wong

doi:10.1055/a-1659-7656

Synlett, Table of Contents

Synlett 2022; 33(01): 34-37
DOI: 10.1055/a-1659-7656

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Bis(η⁵-cyclopentadienyl)[μ-(4b,5,5a-η³:9b,10,10a-η³)-2,3,7,8-tetrakis(trimethylsilyl)benzo[3,4]cyclobuta[1,2-b]biphenylene]-syn-dicobalt (Co–Co), a Dinuclear π-Complex of the Linear [3]Phenylene Framework

Robin Padilla

^aDepartment of Chemistry, University of California at Berkeley, Berkeley, California 94720-1460, USA

,

K. Peter C. Vollhardt ∗

^aDepartment of Chemistry, University of California at Berkeley, Berkeley, California 94720-1460, USA

,

Kendall N. Houk

^bDepartment of Chemistry and Biochemistry, University of California, Los Angeles, California 90095, USA

,

Jonathan J. Wong

^bDepartment of Chemistry and Biochemistry, University of California, Los Angeles, California 90095, USA

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Abstract

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Abstract

The title compound was made by the reaction of the CpCo-complex of 2,3,7,8-tetrakis(trimethylsilyl) linear [3]phenylene, in which the metal coordinates one of the cyclobutadiene rings, with CpCo(C₂H₄)₂. Because of its relative stability, a syn-dicobalt-bound configuration is indicated rather than its anti alternative.

Key words

aromaticity - cobalt - complexation - dinuclear complexes - phenylenes

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References

References and Notes

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11 2,3,7,8-Tetrakis(trimethylsilyl) linear [3]phenylene(CpCo)₂ 6In a glovebox, 2,3,7,8-tetrakis(trimethylsilyl) linear [3]phenylene(CpCo) 1 (85 mg, 0.133 mmol) and CpCo(C₂H₄)₂ (25 mg, 0.139 mmol) were added to a Schlenk flask. The flask was taken out of the glove box, and freshly distilled degassed benzene (15 mL) was added under N₂. The mixture was heated to 70 °C in an oil bath for 23 h and then cooled to r.t. The solvent was removed in vacuo, furnishing a black residue that was filtered rapidly through a plug of neutral alumina (activity III; 2.5 × 3.5 cm), eluting with hexanes–THF (100:1) under N₂. The solvents were again removed in vacuo, and the ensuing black residue was crystallized from acetone–EtOAc (100:1) at –78 °C to give reddish-black crystals; yield: 57 mg (56%). ¹H NMR (400 MHz, acetone-d ₆): δ = 7.36 (s, 4 H), 4.89 (m, 4 H), 4.81 (s, 2 H), 0.39 (s, 36 H). ¹³C NMR (100 MHz, acetone-d ₆): δ = 150.5, 145.4, 125.9, 82.8, 57.1, 53.7, 2.66. MS (FAB): m/z = 762 ([M⁺]). HRMS (EI, 70 eV): m/z [M⁺] calcd for C₄₀H₅₂Co₂Si₄: 762.1810; found: 762.1791. UV/Vis (hexane): λ_max (log ε) = 221 (3.36, sh), 244 (3.44), 286 (3.63), 386 (2.79, sh), 439 nm (2.58).

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