Synthesis of 2,2′,3,3′-Tetramethyl- and 2,2′,3,3′-Tetra-tert-butylfulvalene: Attractive­ Platforms for Dinuclear Transition Metal Fragments, as Exemplified by (η5:η5-2,2′,3,3′-t-Bu4C10H4)M2(CO)n (M = Fe, Ru, Os, Mo) and First X-ray Crystal Structures of Fulvalene Diiron and Diosmium Complexes

Bolin Zhu; Ognjen Š Miljanić; K. Peter C. Vollhardt; Michael J. West

doi:10.1055/s-2005-918438

PAPER

Synthesis of 2,2′,3,3′-Tetramethyl- and 2,2′,3,3′-Tetra-tert-butylfulvalene: Attractive Platforms for Dinuclear Transition Metal Fragments, as Exemplified by (η ⁵:η ⁵-2,2′,3,3′-t-Bu₄C₁₀H₄)M₂(CO)_n (M = Fe, Ru, Os, Mo) and First X-ray Crystal Structures of Fulvalene Diiron and Diosmium Complexes

Bolin Zhu^a,b, Ognjen Š. Miljanić^a,b, K. Peter C. Vollhardt*^a,b, Michael J. West^a,b
^a Center for New Directions in Organic Synthesis, Department of Chemistry, University of California at Berkeley, Berkeley, CA 94720, USA
^b Chemical Sciences Division, Lawrence Berkeley National Laboratory, Berkeley, CA 94720-1460, USA
Fax: +1(510)6435208; e-Mail: kpcv@berkeley.edu;

Abstract

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Abstract

2,2′,3,3′-Tetramethylfulvalene (4) and 2,2′,3,3′-tetra-tert-butylfulvalene (7) were synthesized by two different routes. The potential of these systems to function as ligands to transition metals was explored with the more readily made 7, resulting in the preparation of the dinuclear complexes (η ⁵:η ⁵-t-Bu₄C₁₀H₄)M₂(CO)₄ (M = Fe, Ru, Os, 8-10) and (η ⁵:η ⁵-t-Bu₄C₁₀H₄)Mo₂(CO)₆ (11). The molecular structures of complexes 8 and 10 were determined by X-ray diffraction. Complexes 9 and 10 rearranged on irradiation to their (µ ₂-η ¹:η ⁵-cyclopentadienyl)₂M₂(CO)₄ isomers 12 and 13, respectively, thermally reversible for 12, while 8 was photoinert.

Key words

pentafulvalene - fulvalene complexes - isomerizations - photochemistry - transition metals

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