Synthesis and Reactivity of a Tethered Diene Cyclopentadiene, (C5Me4H)SiMe2(CH2CH=CHCH=CH2), and Its Alkali Metal Salts
Journal of Organometallic Chemistry
Cyclopentadienyl, Tethered diene, Tetramethylcyclopentadienyl, Bent metallocene, Potassium, Titanium
(C5Me4H)SiMe2Cl reacts with (THF)KCH2CH=CHCH=CH2 to form (C5Me4H)SiMe2(CH2CHCHCHCH2) (1). Compound 1 reacts with KH and n-BuLi to make M(C5Me4)SiMe2(CH2CHCHCHCH2), M=K, 2; Li, 3, respectively. Carbon–silicon cleavage occurs when 1 reacts with K to form (C5Me4H)K, which crystallizes from dimethoxyethane as [(C5Me4H)K(DME)]x. This potassium salt has an extended structure which generates bent metallocene (C5Me4H)2K(DME) sub-structures which have 133.9° ring centroidKring centroid angles. Compound 1 reacts with TiCl4 to make (C5Me4H)TiCl3 (5), which has a piano stool structure.
Evans, William J.; Giarikos, Dimitri; and Ziller, Joseph W., "Synthesis and Reactivity of a Tethered Diene Cyclopentadiene, (C5Me4H)SiMe2(CH2CH=CHCH=CH2), and Its Alkali Metal Salts" (2003). Chemistry and Physics Faculty Articles. 65.