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

Research output: Contribution to journalArticle

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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

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Photochemistry
Photochemical reactions
Photolysis
Carbon Monoxide
photochemical reactions
photolysis
Tantalum
synthesis
matrices
tantalum
Niobium
niobium
Molecular structure
molecular structure
Ligands
routes
Nuclear magnetic resonance
Annealing
Derivatives
Glass

Keywords

  • Niobium
  • Photochemistry
  • Tantalum

ASJC Scopus subject areas

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

Cite this

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

In: Journal of Organometallic Chemistry, Vol. 557, No. 1, 20.04.1998, p. 77-92.

Research output: Contribution to journalArticle

Bitterwolf, TE, Gallagher, S, Bays, JT, Scallorn, B, Rheingold, AL, Guzei, IA, 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, vol. 557, no. 1, pp. 77-92.
Bitterwolf, Thomas E. ; Gallagher, Skip ; Bays, J. Timothy ; Scallorn, Bruce ; Rheingold, Arnold L. ; Guzei, Ilia A. ; Liable-Sands, Louise ; Linehan, John. / 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. In: Journal of Organometallic Chemistry. 1998 ; Vol. 557, No. 1. pp. 77-92.
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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) {\AA}, b=6.937(1) {\AA}, c=12.706(2) {\AA}, α=90.42(1)°, β=91.07(1)°, γ=105.560(8)°, V=574.71(12) {\AA}3, Z=2, R(F)=2.82; (acetylCp)Nb(CO)4: monoclinic, P21/c, a=10.316(2) {\AA}, b=14.490(3) {\AA}, c=7.957(3) {\AA}, β=94.68(2)°, V=1185.4(4) {\AA}3, Z=4, R(F)=2.58; (Cp)Ta(CO)4: orthorhombic, Pnma, a=7.756(1) {\AA}, b=12.159(2) {\AA}, c=10.580(1) {\AA}, V=997.7(2) {\AA}3, Z=4, R(F)=2.60; (indenyl)Ta(CO)4: monoclinic, P21/n, a=6.602(2) {\AA}, b=12.399(1) {\AA}, c=7.4775(9) {\AA}, β=92.05(2)°, V=611.2(2) {\AA}3, Z=2, R(F)=3.05; and (benzoylCp)Ta(CO)4: monoclinic, P21/c, a=12.552(10) {\AA}, b=6.5247(2) {\AA}, c=18.4682(2) {\AA}, β=98.9152(4)°, V=1494.24(5) {\AA}3, 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.",
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T1 - 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

AU - Bitterwolf, Thomas E.

AU - Gallagher, Skip

AU - Bays, J. Timothy

AU - Scallorn, Bruce

AU - Rheingold, Arnold L.

AU - Guzei, Ilia A.

AU - Liable-Sands, Louise

AU - Linehan, John

PY - 1998/4/20

Y1 - 1998/4/20

N2 - 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.

AB - 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.

KW - Niobium

KW - Photochemistry

KW - Tantalum

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