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

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

Pacific Northwest National Laboratory

Research output: Contribution to journal › Article

20 Citations (Scopus)

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 language	English
Pages (from-to)	77-92
Number of pages	16
Journal	Journal of Organometallic Chemistry
Volume	557
Issue number	1
Publication status	Published - Apr 20 1998

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Keywords

Niobium
Photochemistry
Tantalum

ASJC Scopus subject areas

Biochemistry
Inorganic Chemistry
Organic Chemistry
Physical and Theoretical Chemistry
Materials Chemistry

Cite this

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.

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 journal › Article

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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title = "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",

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.",

keywords = "Niobium, Photochemistry, Tantalum",

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

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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.

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