An investigation into the photochemical reactions of MCp(CO)4 (Cp = η5-C5H5) and M(η5-C9H7)(CO)4 (η5-C9H7 = indenyl; M = Nb or Ta) with CO, H2 and N2 in solution at room temperature

G. I. Childs; D. C. Grills; S. Gallagher; T. E. Bitterwolf; M. W. George

doi:10.1039/b010033l

An investigation into the photochemical reactions of MCp(CO)₄ (Cp = η⁵-C₅H₅) and M(η⁵-C₉H₇)(CO)₄ (η⁵-C₉H₇ = indenyl; M = Nb or Ta) with CO, H₂ and N₂ in solution at room temperature

G. I. Childs, D. C. Grills, S. Gallagher, T. E. Bitterwolf, M. W. George

Research output: Journal Publication › Article › peer-review

13 Citations (Scopus)

Abstract

Time resolved step-scan FTIR spectroscopy (s²-FTIR) has been used to characterise MCp′(CO)₃L (Cp′ = Cp or indenyl (η⁵-C₉H₇); M = Nb or Ta; L = n-heptane, H₂ or N₂) in solution at room temperature. TaCp′(CO)₄ formed the classical dihydrides, TaCp′(CO)₃H₂ upon irradiation in n-heptane saturated with H₂. However, photolysis of Nb(η⁵-C₉H₇)(CO)₄ under the same conditions led to the non-classical complex, Nb(η⁵-C₉H₇)(CO)₃(η ²-H₂), whereas irradiation of NbCp(CO)₄ resulted in both NbCp(CO)₃H₂ and NbCp(CO)₃(η²-H₂). Photolysis of MCp′(CO)₄ in n-heptane saturated with N₂ resulted in formation of MCp′(CO)₃(N₂) in all cases. No evidence for disubstitution of these complexes was obtained in these s²-FTIR experiments. The rate constants for the reaction of M(η⁵-C₉H₇)(CO)₃(n-C ₇H₁₆) with CO, H₂ and N₂ have been determined. Comparison of these rate constants with those obtained for the analogous cyclopentadienyl complexes showed that the indenyl complexes are more reactive (ca. 10 times). Additionally, the Nb(η⁵-C₉H₇)(CO)₃(L) (L = η²-H₂ or N₂) complexes were found to be less stable (ca. 20-30 times) than NbCp(CO)₃(L), and Ta(η⁵-C₉H₇)(CO)₃(N ₂) was more reactive (ca. 25 times) than TaCp(CO)₃(N₂).

Original language	English
Pages (from-to)	1711-1717
Number of pages	7
Journal	Journal of the Chemical Society. Dalton Transactions
Issue number	11
DOIs	https://doi.org/10.1039/b010033l
Publication status	Published - 2001
Externally published	Yes

ASJC Scopus subject areas

General Chemistry

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Childs, G. I., Grills, D. C., Gallagher, S., Bitterwolf, T. E., & George, M. W. (2001). An investigation into the photochemical reactions of MCp(CO)₄ (Cp = η⁵-C₅H₅) and M(η⁵-C₉H₇)(CO)₄ (η⁵-C₉H₇ = indenyl; M = Nb or Ta) with CO, H₂ and N₂ in solution at room temperature. Journal of the Chemical Society. Dalton Transactions, (11), 1711-1717. https://doi.org/10.1039/b010033l

@article{9ba228b66e0b46b192ee36f37f64cf70,

title = "An investigation into the photochemical reactions of MCp(CO)4 (Cp = η5-C5H5) and M(η5-C9H7)(CO)4 (η5-C9H7 = indenyl; M = Nb or Ta) with CO, H2 and N2 in solution at room temperature",

abstract = "Time resolved step-scan FTIR spectroscopy (s2-FTIR) has been used to characterise MCp′(CO)3L (Cp′ = Cp or indenyl (η5-C9H7); M = Nb or Ta; L = n-heptane, H2 or N2) in solution at room temperature. TaCp′(CO)4 formed the classical dihydrides, TaCp′(CO)3H2 upon irradiation in n-heptane saturated with H2. However, photolysis of Nb(η5-C9H7)(CO)4 under the same conditions led to the non-classical complex, Nb(η5-C9H7)(CO)3(η 2-H2), whereas irradiation of NbCp(CO)4 resulted in both NbCp(CO)3H2 and NbCp(CO)3(η2-H2). Photolysis of MCp′(CO)4 in n-heptane saturated with N2 resulted in formation of MCp′(CO)3(N2) in all cases. No evidence for disubstitution of these complexes was obtained in these s2-FTIR experiments. The rate constants for the reaction of M(η5-C9H7)(CO)3(n-C 7H16) with CO, H2 and N2 have been determined. Comparison of these rate constants with those obtained for the analogous cyclopentadienyl complexes showed that the indenyl complexes are more reactive (ca. 10 times). Additionally, the Nb(η5-C9H7)(CO)3(L) (L = η2-H2 or N2) complexes were found to be less stable (ca. 20-30 times) than NbCp(CO)3(L), and Ta(η5-C9H7)(CO)3(N 2) was more reactive (ca. 25 times) than TaCp(CO)3(N2).",

author = "Childs, {G. I.} and Grills, {D. C.} and S. Gallagher and Bitterwolf, {T. E.} and George, {M. W.}",

year = "2001",

doi = "10.1039/b010033l",

language = "English",

pages = "1711--1717",

journal = "Journal of the Chemical Society. Dalton Transactions",

issn = "1470-479X",

publisher = "Royal Society of Chemistry",

number = "11",

}

An investigation into the photochemical reactions of MCp(CO)₄ (Cp = η⁵-C₅H₅) and M(η⁵-C₉H₇)(CO)₄ (η⁵-C₉H₇ = indenyl; M = Nb or Ta) with CO, H₂ and N₂ in solution at room temperature. / Childs, G. I.; Grills, D. C.; Gallagher, S. et al.
In: Journal of the Chemical Society. Dalton Transactions, No. 11, 2001, p. 1711-1717.

Research output: Journal Publication › Article › peer-review

TY - JOUR

T1 - An investigation into the photochemical reactions of MCp(CO)4 (Cp = η5-C5H5) and M(η5-C9H7)(CO)4 (η5-C9H7 = indenyl; M = Nb or Ta) with CO, H2 and N2 in solution at room temperature

AU - Childs, G. I.

AU - Grills, D. C.

AU - Gallagher, S.

AU - Bitterwolf, T. E.

AU - George, M. W.

PY - 2001

Y1 - 2001

N2 - Time resolved step-scan FTIR spectroscopy (s2-FTIR) has been used to characterise MCp′(CO)3L (Cp′ = Cp or indenyl (η5-C9H7); M = Nb or Ta; L = n-heptane, H2 or N2) in solution at room temperature. TaCp′(CO)4 formed the classical dihydrides, TaCp′(CO)3H2 upon irradiation in n-heptane saturated with H2. However, photolysis of Nb(η5-C9H7)(CO)4 under the same conditions led to the non-classical complex, Nb(η5-C9H7)(CO)3(η 2-H2), whereas irradiation of NbCp(CO)4 resulted in both NbCp(CO)3H2 and NbCp(CO)3(η2-H2). Photolysis of MCp′(CO)4 in n-heptane saturated with N2 resulted in formation of MCp′(CO)3(N2) in all cases. No evidence for disubstitution of these complexes was obtained in these s2-FTIR experiments. The rate constants for the reaction of M(η5-C9H7)(CO)3(n-C 7H16) with CO, H2 and N2 have been determined. Comparison of these rate constants with those obtained for the analogous cyclopentadienyl complexes showed that the indenyl complexes are more reactive (ca. 10 times). Additionally, the Nb(η5-C9H7)(CO)3(L) (L = η2-H2 or N2) complexes were found to be less stable (ca. 20-30 times) than NbCp(CO)3(L), and Ta(η5-C9H7)(CO)3(N 2) was more reactive (ca. 25 times) than TaCp(CO)3(N2).

AB - Time resolved step-scan FTIR spectroscopy (s2-FTIR) has been used to characterise MCp′(CO)3L (Cp′ = Cp or indenyl (η5-C9H7); M = Nb or Ta; L = n-heptane, H2 or N2) in solution at room temperature. TaCp′(CO)4 formed the classical dihydrides, TaCp′(CO)3H2 upon irradiation in n-heptane saturated with H2. However, photolysis of Nb(η5-C9H7)(CO)4 under the same conditions led to the non-classical complex, Nb(η5-C9H7)(CO)3(η 2-H2), whereas irradiation of NbCp(CO)4 resulted in both NbCp(CO)3H2 and NbCp(CO)3(η2-H2). Photolysis of MCp′(CO)4 in n-heptane saturated with N2 resulted in formation of MCp′(CO)3(N2) in all cases. No evidence for disubstitution of these complexes was obtained in these s2-FTIR experiments. The rate constants for the reaction of M(η5-C9H7)(CO)3(n-C 7H16) with CO, H2 and N2 have been determined. Comparison of these rate constants with those obtained for the analogous cyclopentadienyl complexes showed that the indenyl complexes are more reactive (ca. 10 times). Additionally, the Nb(η5-C9H7)(CO)3(L) (L = η2-H2 or N2) complexes were found to be less stable (ca. 20-30 times) than NbCp(CO)3(L), and Ta(η5-C9H7)(CO)3(N 2) was more reactive (ca. 25 times) than TaCp(CO)3(N2).

UR - http://www.scopus.com/inward/record.url?scp=0034742995&partnerID=8YFLogxK

U2 - 10.1039/b010033l

DO - 10.1039/b010033l

M3 - Article

AN - SCOPUS:0034742995

SN - 1470-479X

SP - 1711

EP - 1717

JO - Journal of the Chemical Society. Dalton Transactions

JF - Journal of the Chemical Society. Dalton Transactions

IS - 11

ER -

An investigation into the photochemical reactions of MCp(CO)₄ (Cp = η⁵-C₅H₅) and M(η⁵-C₉H₇)(CO)₄ (η⁵-C₉H₇ = indenyl; M = Nb or Ta) with CO, H₂ and N₂ in solution at room temperature

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