153658-03-8Relevant articles and documents
Iridium η4-1,5-cyclooctadiene and 1,2-η2,6-σ-cycloocta-1,4-dienyl complexes. Deprotonation of coordinated 1,5-cyclooctadiene by strong and weak bases
Gull, Anne M.,Fanwick, Phillip E.,Kubiak, Clifford P.
, p. 2121 - 2125 (2008/10/08)
The reaction of [Ir(η4-1,5-cyclooctadiene)Cl]2 with 2 equiv of triphos [(Ph2PCH2CH2)2PPh] in methylene chloride yields [Ir(triphos)(η4-1,5-cyclooctadiene)][Cl] (1), which upon reaction with various bases [KOH, NaOCH3, NaOC6H5, NaOC6H4-p-CH3, NaOC6H4-p-C(CH3)3, N(C2H5)3, pyridine, N,N,N′,N′-tetramethyl-1,8-naphthalenediamine (Proton Sponge)] in tetrahydrofuran solutions affords the neutral deprotonated complex, Ir(triphos)(1,2-η2,6-σ-cycloocta-1,4-dienyl) (2). X-ray structure determinations of 1 and 2 were undertaken. Complex 1 crystallizes in the monoclinic space group P21/c with a = 15.165(2) A?, b = 10.791(2) A?, c = 23.488(2) A?, V = 3843(2) A?3, Z = 4, and Dcalc = 1.535 g/cm3. The structure was refined to R = 0.029 and Rw = 0.038 for 428 variables and 4043 observations. Complex 2 crystallizes in monoclinic space group Cc with a = 9.5782(8) A?, b = 39.313(5) A?, c = 11.252(2) A?, V = 3911(4) A?3, Z = 4, and Dcalc = 1.560 g/cm3. The structure was refined to R = 0.027 and Rw = 0.034 for 425 variables and 2301 observations. The mechanism of formation of 2 by deprotonation of 1 is discussed.
