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 C. Linehan

doi:10.1016/S0022-328X(97)00735-3

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 C. Linehan

Pacific Northwest National Laboratory

Research output: Contribution to journal › Article › peer-review

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
DOIs	https://doi.org/10.1016/S0022-328X(97)00735-3
Publication status	Published - Apr 20 1998

Keywords

Niobium
Photochemistry
Tantalum

ASJC Scopus subject areas

Biochemistry
Physical and Theoretical Chemistry
Organic Chemistry
Inorganic Chemistry
Materials Chemistry

Access to Document

10.1016/S0022-328X(97)00735-3

Fingerprint Dive into the research topics of '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'. Together they form a unique fingerprint.

Cite this

Bitterwolf, T. E., Gallagher, S., Bays, J. T., Scallorn, B., Rheingold, A. L., Guzei, I. A., Liable-Sands, L., & Linehan, J. C. (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. https://doi.org/10.1016/S0022-328X(97)00735-3

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 C.

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

Research output: Contribution to journal › Article › peer-review

Bitterwolf, TE, Gallagher, S, Bays, JT, Scallorn, B, Rheingold, AL, Guzei, IA, Liable-Sands, L & Linehan, JC 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. https://doi.org/10.1016/S0022-328X(97)00735-3

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

@article{38b10411bfa04fb4ad64c818461182d5,

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 Linehan, {John C.}",

note = "Funding Information: Thomas E. Bitterwolf thanks the Research Corporation for their generous support for the purchase of the Perkin Elmer FT-IR Spectrum 1000 Spectrometer and the University of Idaho Research Council for funding this research. The University of Delaware acknowledges the National Science Foundation for their support of the purchase of the CCD-based diffractometer (Grant CHE-9628768). Copyright: Copyright 2017 Elsevier B.V., All rights reserved.",

year = "1998",

month = apr,

day = "20",

doi = "10.1016/S0022-328X(97)00735-3",

language = "English",

volume = "557",

pages = "77--92",

journal = "Journal of Organometallic Chemistry",

issn = "0022-328X",

publisher = "Elsevier",

number = "1",

}

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 C.

N1 - Funding Information: Thomas E. Bitterwolf thanks the Research Corporation for their generous support for the purchase of the Perkin Elmer FT-IR Spectrum 1000 Spectrometer and the University of Idaho Research Council for funding this research. The University of Delaware acknowledges the National Science Foundation for their support of the purchase of the CCD-based diffractometer (Grant CHE-9628768). Copyright: Copyright 2017 Elsevier B.V., All rights reserved.

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

U2 - 10.1016/S0022-328X(97)00735-3

DO - 10.1016/S0022-328X(97)00735-3

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 -