Unexpected carbon-carbon bond cleavage in the reactions of the pentagonal bipyramidal cluster Fe3(CO)6(μ-CO)2[μ 3-η4-{RCC(Et)C(Et)CR}] with styrene. Synthesis and X-ray structure of Fe3(CO)6[μ3- η4-{EtC2CR}]2 (R = CH3(=CH 2)

Giuliana Gervasio; Domenica Marabello; Enrico Sappa; Andrea Secco

doi:10.1007/s10876-007-0162-5

Unexpected carbon-carbon bond cleavage in the reactions of the pentagonal bipyramidal cluster Fe₃(CO)₆(μ-CO)₂[μ ₃-η⁴-{RCC(Et)C(Et)CR}] with styrene. Synthesis and X-ray structure of Fe₃(CO)₆[μ₃- η⁴-{EtC₂CR}]₂ (R = CH₃(=CH ₂)

Giuliana Gervasio, Domenica Marabello, Enrico Sappa, Andrea Secco

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

Abstract

The thermal reactions of 2-methyl-1-hexen-3-yne [CH₃CH ₂C = +CC(=CH₂)CH₃, metey] with Fe ₃(CO)₁₂ have been studied: cluster opening or fragmentation and alkyne dimerization occur. Main products are the open triangular isomers [Fe₃(CO)₆(μ-CO)₂{CH ₃(=CH₂)CC(Et)C(Et)C(=CH₂)CH₃}] (complex 3a) and [Fe₃(CO)₆(μ-CO)₂{C(Et) CCH₃(=CH₂)C(Et)CCH₃(=CH₂)}] (complex 3b). The structure and isomerism of the complexes has been confirmed by X-ray studies. The minor products of the reaction have been characterized by spectroscopic techniques. An attempt at exploiting the reactivity of the "free" C=C bonds of the coordinated ene-yne was made: complex 3a was reacted with styrene under thermal conditions. Unexpectedly considerable yields of the closed triangular cluster [Fe₃(CO)₆{EtC ₂C(=CH₂)CH₃}₂] (complex 5) have been obtained. This behaviour had not been previously observed. The unprecedented structure of complex 5 has been confirmed with an X-ray study.

Original language	English
Pages (from-to)	197-208
Number of pages	12
Journal	Journal of Cluster Science
Volume	19
Issue number	1
DOIs	https://doi.org/10.1007/s10876-007-0162-5
Publication status	Published - Mar 2008
Externally published	Yes

Keywords

Carbon-carbon bond cleavage
Metallacycles
Tri-iron clusters
Vinyl-acetylene (ene-yne) ligands
X-ray structure determination

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Gervasio, G., Marabello, D., Sappa, E., & Secco, A. (2008). Unexpected carbon-carbon bond cleavage in the reactions of the pentagonal bipyramidal cluster Fe₃(CO)₆(μ-CO)₂[μ ₃-η⁴-{RCC(Et)C(Et)CR}] with styrene. Synthesis and X-ray structure of Fe₃(CO)₆[μ₃- η⁴-{EtC₂CR}]₂ (R = CH₃(=CH ₂). Journal of Cluster Science, 19(1), 197-208. https://doi.org/10.1007/s10876-007-0162-5

@article{02fde6a120a845ad89dabee9a4817904,

title = "Unexpected carbon-carbon bond cleavage in the reactions of the pentagonal bipyramidal cluster Fe3(CO)6(μ-CO)2[μ 3-η4-{RCC(Et)C(Et)CR}] with styrene. Synthesis and X-ray structure of Fe3(CO)6[μ3- η4-{EtC2CR}]2 (R = CH3(=CH 2)",

abstract = "The thermal reactions of 2-methyl-1-hexen-3-yne [CH3CH 2C = +CC(=CH2)CH3, metey] with Fe 3(CO)12 have been studied: cluster opening or fragmentation and alkyne dimerization occur. Main products are the open triangular isomers [Fe3(CO)6(μ-CO)2{CH 3(=CH2)CC(Et)C(Et)C(=CH2)CH3}] (complex 3a) and [Fe3(CO)6(μ-CO)2{C(Et) CCH3(=CH2)C(Et)CCH3(=CH2)}] (complex 3b). The structure and isomerism of the complexes has been confirmed by X-ray studies. The minor products of the reaction have been characterized by spectroscopic techniques. An attempt at exploiting the reactivity of the {"}free{"} C=C bonds of the coordinated ene-yne was made: complex 3a was reacted with styrene under thermal conditions. Unexpectedly considerable yields of the closed triangular cluster [Fe3(CO)6{EtC 2C(=CH2)CH3}2] (complex 5) have been obtained. This behaviour had not been previously observed. The unprecedented structure of complex 5 has been confirmed with an X-ray study.",

keywords = "Carbon-carbon bond cleavage, Metallacycles, Tri-iron clusters, Vinyl-acetylene (ene-yne) ligands, X-ray structure determination",

author = "Giuliana Gervasio and Domenica Marabello and Enrico Sappa and Andrea Secco",

year = "2008",

month = mar,

doi = "10.1007/s10876-007-0162-5",

language = "English",

volume = "19",

pages = "197--208",

journal = "Journal of Cluster Science",

issn = "1040-7278",

publisher = "Springer New York",

number = "1",

}

Gervasio, G, Marabello, D, Sappa, E & Secco, A 2008, 'Unexpected carbon-carbon bond cleavage in the reactions of the pentagonal bipyramidal cluster Fe₃(CO)₆(μ-CO)₂[μ ₃-η⁴-{RCC(Et)C(Et)CR}] with styrene. Synthesis and X-ray structure of Fe₃(CO)₆[μ₃- η⁴-{EtC₂CR}]₂ (R = CH₃(=CH ₂)', Journal of Cluster Science, vol. 19, no. 1, pp. 197-208. https://doi.org/10.1007/s10876-007-0162-5

Unexpected carbon-carbon bond cleavage in the reactions of the pentagonal bipyramidal cluster Fe₃(CO)₆(μ-CO)₂[μ ₃-η⁴-{RCC(Et)C(Et)CR}] with styrene. Synthesis and X-ray structure of Fe₃(CO)₆[μ₃- η⁴-{EtC₂CR}]₂ (R = CH₃(=CH ₂). / Gervasio, Giuliana; Marabello, Domenica; Sappa, Enrico et al.
In: Journal of Cluster Science, Vol. 19, No. 1, 03.2008, p. 197-208.

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

TY - JOUR

T1 - Unexpected carbon-carbon bond cleavage in the reactions of the pentagonal bipyramidal cluster Fe3(CO)6(μ-CO)2[μ 3-η4-{RCC(Et)C(Et)CR}] with styrene. Synthesis and X-ray structure of Fe3(CO)6[μ3- η4-{EtC2CR}]2 (R = CH3(=CH 2)

AU - Gervasio, Giuliana

AU - Marabello, Domenica

AU - Sappa, Enrico

AU - Secco, Andrea

PY - 2008/3

Y1 - 2008/3

N2 - The thermal reactions of 2-methyl-1-hexen-3-yne [CH3CH 2C = +CC(=CH2)CH3, metey] with Fe 3(CO)12 have been studied: cluster opening or fragmentation and alkyne dimerization occur. Main products are the open triangular isomers [Fe3(CO)6(μ-CO)2{CH 3(=CH2)CC(Et)C(Et)C(=CH2)CH3}] (complex 3a) and [Fe3(CO)6(μ-CO)2{C(Et) CCH3(=CH2)C(Et)CCH3(=CH2)}] (complex 3b). The structure and isomerism of the complexes has been confirmed by X-ray studies. The minor products of the reaction have been characterized by spectroscopic techniques. An attempt at exploiting the reactivity of the "free" C=C bonds of the coordinated ene-yne was made: complex 3a was reacted with styrene under thermal conditions. Unexpectedly considerable yields of the closed triangular cluster [Fe3(CO)6{EtC 2C(=CH2)CH3}2] (complex 5) have been obtained. This behaviour had not been previously observed. The unprecedented structure of complex 5 has been confirmed with an X-ray study.

AB - The thermal reactions of 2-methyl-1-hexen-3-yne [CH3CH 2C = +CC(=CH2)CH3, metey] with Fe 3(CO)12 have been studied: cluster opening or fragmentation and alkyne dimerization occur. Main products are the open triangular isomers [Fe3(CO)6(μ-CO)2{CH 3(=CH2)CC(Et)C(Et)C(=CH2)CH3}] (complex 3a) and [Fe3(CO)6(μ-CO)2{C(Et) CCH3(=CH2)C(Et)CCH3(=CH2)}] (complex 3b). The structure and isomerism of the complexes has been confirmed by X-ray studies. The minor products of the reaction have been characterized by spectroscopic techniques. An attempt at exploiting the reactivity of the "free" C=C bonds of the coordinated ene-yne was made: complex 3a was reacted with styrene under thermal conditions. Unexpectedly considerable yields of the closed triangular cluster [Fe3(CO)6{EtC 2C(=CH2)CH3}2] (complex 5) have been obtained. This behaviour had not been previously observed. The unprecedented structure of complex 5 has been confirmed with an X-ray study.

KW - Carbon-carbon bond cleavage

KW - Metallacycles

KW - Tri-iron clusters

KW - Vinyl-acetylene (ene-yne) ligands

KW - X-ray structure determination

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U2 - 10.1007/s10876-007-0162-5

DO - 10.1007/s10876-007-0162-5

M3 - Article

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JO - Journal of Cluster Science

JF - Journal of Cluster Science

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