Improved synthesis of (η5-CpR)M(CO)4 compounds and the Nujol matrix photochemistry of (η5-C5H5)M(CO)4 and (η5-C9H7)M(CO)4, where M=Nb and Ta

Thomas E. Bitterwolf, Skip Gallagher, J. Timothy Bays, Bruce Scallorn, Arnold L. Rheingold, Ilia A. Guzei, Louise Liable-Sands, John Linehan

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Abstract

Improved preparative routes for cyclopentadienyl (Cp) and substituted Cp(CO)4 derivatives of niobium and tantalum and their precursors are described. New compounds are fully characterized by IR, NMR, and elemental analysis. The molecular structures of five compounds were determined: (vinylCp)Nb(CO)4: triclinic, Pī, a=6.770(1) Å, b=6.937(1) Å, c=12.706(2) Å, α=90.42(1)°, β=91.07(1)°, γ=105.560(8)°, V=574.71(12) Å3, Z=2, R(F)=2.82; (acetylCp)Nb(CO)4: monoclinic, P21/c, a=10.316(2) Å, b=14.490(3) Å, c=7.957(3) Å, β=94.68(2)°, V=1185.4(4) Å3, Z=4, R(F)=2.58; (Cp)Ta(CO)4: orthorhombic, Pnma, a=7.756(1) Å, b=12.159(2) Å, c=10.580(1) Å, V=997.7(2) Å3, Z=4, R(F)=2.60; (indenyl)Ta(CO)4: monoclinic, P21/n, a=6.602(2) Å, b=12.399(1) Å, c=7.4775(9) Å, β=92.05(2)°, V=611.2(2) Å3, Z=2, R(F)=3.05; and (benzoylCp)Ta(CO)4: monoclinic, P21/c, a=12.552(10) Å, b=6.5247(2) Å, c=18.4682(2) Å, β=98.9152(4)°, V=1494.24(5) Å3, Z=4, RF)=2.83 are reported. Photolysis of CpMCO)4 and indenyl)MCO)4, where M=Nb and Ta, in Nujol glass matrices were found to result in loss of one to three CO ligands as a function of the wavelength of the incident light. Annealing or reverse photolysis resulted in reversal of these CO-loss reactions.

Original languageEnglish
Pages (from-to)77-92
Number of pages16
JournalJournal of Organometallic Chemistry
Volume557
Issue number1
Publication statusPublished - Apr 20 1998

Keywords

  • Niobium
  • Photochemistry
  • Tantalum

ASJC Scopus subject areas

  • Biochemistry
  • Inorganic Chemistry
  • Organic Chemistry
  • Physical and Theoretical Chemistry
  • Materials Chemistry

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    Bitterwolf, T. E., Gallagher, S., Bays, J. T., Scallorn, B., Rheingold, A. L., Guzei, I. A., Liable-Sands, L., & Linehan, J. (1998). Improved synthesis of (η5-CpR)M(CO)4 compounds and the Nujol matrix photochemistry of (η5-C5H5)M(CO)4 and (η5-C9H7)M(CO)4, where M=Nb and Ta. Journal of Organometallic Chemistry, 557(1), 77-92.