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
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
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TY - JOUR
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
UR - http://www.scopus.com/inward/record.url?scp=0002137715&partnerID=8YFLogxK
UR - http://www.scopus.com/inward/citedby.url?scp=0002137715&partnerID=8YFLogxK
M3 - Article
AN - SCOPUS:0002137715
VL - 557
SP - 77
EP - 92
JO - Journal of Organometallic Chemistry
JF - Journal of Organometallic Chemistry
SN - 0022-328X
IS - 1
ER -