Ring functionalized cyclopentadienyl derivatives of niobium and tantalum: molecular structures of (η⁵-C₅H₄-CO₂CH₃)M(CO)₄ where M

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• 作者：Bitterwolf ; Thomas E. ; Gallagher ; Skip ; Rheingold ; Arnold L. ; Yap ; Glenn P.A.
• 刊名：Journal of Organometallic Chemistry
• 出版年：1997
• 出版时间：October 30, 1997
• 年：1997
• 卷：545-546
• 期：Complete
• 页码：27-33
• 全文大小：686 K

文摘

Reaction of Na[M₂(μ-Cl)₃(CO)₈], where M = Nb or Ta, with NaC₅H₄R, where R = COCH₃, CO₂CH₃, CO₂C₂H₅, COC₆H₅, COCH₂C₆H₅, LiC₅H₄C(CH₃)CH₂, or NaC₉H₇ gives the corresponding (η⁵-C₅H₄R)M(CO)₄, or (η⁵-C₉H₇)M(CO)₄ compounds in good yield. NaC₅H₄COCH₂C₆H₅, a new cyclopentadienyl synthon, was used to prepare TlC₅H₄COCH₂C₆H₅, and (η⁵-C₅H₄COCH₂C₆H₅)Mn(CO)₃. The latter was fully characterized as a model compound for the new ligand. The niobium and tantalum compounds are air-stable as solids but readily undergo oxidation in solution. Compounds were characterized by IR, ¹H and ¹³C NMR spectroscopies, and elemental analyses. Molecular structures of three compounds were determined. (η⁵-C₅H₄CO₂CH₃)Nb(CO)₄: monoclinic, P2₁/c, a = 12.664(6) Å, b = 6.390(3) Å, c, = 15.355(9) Å, β = 97.81(4)°, V = 1231(1) ų, Z = 4, and R(F) = 3.90 % . (η⁵-C₅H₄CO₂CH₃)Ta(CO)₄: monoclinic, P2₁/c, a = 12.612(4) Å, b = 6.399(1) Å, c, = 15.273(6) Å, β = 97.89(3)°, V = 1220.9(4) U³, Z = 4, and R(F) = 5.67 % . (η⁵-C₉H₇)Nb(CO)₄: monoclinic, P2₁/c, a = 16.353(2) Å, b = 7.959(1) Å, c,= 12.778(4) Å, β = 106.14(2)°, = 1597.7(6) ų, Z = 4, and R(F) = 2.48 % .