Transient and Matrix Photochemistry of Fe(dmpe)2H2 (dmpe = Me2PCH2CH2PMe2): Dynamics of C-H and H-H Activation

Michael K. Whittlesey; Roger J. Mawby; Robert Osman; Robin N. Perutz; Leslie D. Field; Matthew P. Wilkinson; Michael W. George

doi:10.1021/ja00072a016

Transient and Matrix Photochemistry of Fe(dmpe)₂H₂ (dmpe = Me₂PCH₂CH₂PMe₂): Dynamics of C-H and H-H Activation

Michael K. Whittlesey, Roger J. Mawby, Robert Osman, Robin N. Perutz, Leslie D. Field, Matthew P. Wilkinson, Michael W. George

Research output: Journal Publication › Article › peer-review

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Abstract

The transient photochemistry in solution and low-temperature matrix photochemistry of Fe(dmpe)₂H₂ (dmpe = Me₂PCH₂CH₂PMe₂) are reported; this compound is uniquely effective among first-row transition metal complexes in its ability to activate C-H bonds. Pulsed laser photolysis (308 nm) of alkane solutions of Fe(dmpe)₂H₂ at ambient temperature generates Fe(dmpe)₂ (λ_max = 355 nm) within 30 ns. In the absence of added quenchers, the latter decays by reaction with the alkane solvent (in pentane, k_obs = 630 s⁻¹ at 297 K, ΔH^‡ = 25.0 ± 5.9 kJ mol⁻¹, ΔS^‡ = −125 ± 22 J K⁻¹ mol⁻¹). The pseudo-first-order rate constants very with alkane by a factor of ca. 4. Fe(dmpe)₂ is quenched by added reagents with second-order rate constants in the range 10⁹-10⁴ dm³ mol⁻¹ s⁻¹, decreasing in the order CO ≫ H² > C₂H₄ > N₂ > cyclopentene > Et₃SiH. The activation parameters for reaction with Et₃SiH are ΔH^‡ = 22.4 ± 1.8 kJ mol^–1, ΔS^‡ = −87 ± 6 J K⁻¹ mol⁻¹. The product of reaction with CO is demonstrated by time-resolved IR spectroscopy to be Fe(dmpe)₂(CO), which forms at the same rate as the transient decays. The reactions with arenes (benzene and toluene) in cyclohexane exhibit saturation kinetics which are interpreted in terms of reversible formation of Fe(dmpe)₂(arene), followed by conversion to Fe(dmpe)₂(aryl)H with rate constants of ca. 10⁶ s⁻¹. UV irradiation of Fe(dmpe)₂H₂ in Ar matrices at 12 K also yields Fe(dmpe)₂ (UV and IR detection). The reaction may be partially reversed by selective photolysis. Irradiation in CO- or N₂-doped matrices yields Fe(dmpe)₂L (L = CO, N₂): in a methane matrix the photoproduct is Fe(dmpe)₂(CH₃)H. Fe(dmpe)₂ differs drastically from Ru(dmpe)₂ in its absorption spectrum and its reactivity. Most notably, the rate constant for reaction with H₂ is a factor of 7500 smaller for Fe(dmpe)₂ than for Ru(dmpe)₂. In contrast, reactions of both complexes with CO are diffusion-controlled.

Original language	English
Pages (from-to)	8627-8637
Number of pages	11
Journal	Journal of the American Chemical Society
Volume	115
Issue number	19
DOIs	https://doi.org/10.1021/ja00072a016
Publication status	Published - 1 Sept 1993
Externally published	Yes

ASJC Scopus subject areas

Catalysis
General Chemistry
Biochemistry
Colloid and Surface Chemistry

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10.1021/ja00072a016

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@article{094a70d836954146b07314b544120894,

title = "Transient and Matrix Photochemistry of Fe(dmpe)2H2 (dmpe = Me2PCH2CH2PMe2): Dynamics of C-H and H-H Activation",

abstract = "The transient photochemistry in solution and low-temperature matrix photochemistry of Fe(dmpe)2H2 (dmpe = Me2PCH2CH2PMe2) are reported; this compound is uniquely effective among first-row transition metal complexes in its ability to activate C-H bonds. Pulsed laser photolysis (308 nm) of alkane solutions of Fe(dmpe)2H2 at ambient temperature generates Fe(dmpe)2 (λmax = 355 nm) within 30 ns. In the absence of added quenchers, the latter decays by reaction with the alkane solvent (in pentane, kobs = 630 s−1 at 297 K, ΔH‡ = 25.0 ± 5.9 kJ mol−1, ΔS‡ = −125 ± 22 J K−1 mol−1). The pseudo-first-order rate constants very with alkane by a factor of ca. 4. Fe(dmpe)2 is quenched by added reagents with second-order rate constants in the range 109-104 dm3 mol−1 s−1, decreasing in the order CO ≫ H2 > C2H4 > N2 > cyclopentene > Et3SiH. The activation parameters for reaction with Et3SiH are ΔH‡ = 22.4 ± 1.8 kJ mol–1, ΔS‡ = −87 ± 6 J K−1 mol−1. The product of reaction with CO is demonstrated by time-resolved IR spectroscopy to be Fe(dmpe)2(CO), which forms at the same rate as the transient decays. The reactions with arenes (benzene and toluene) in cyclohexane exhibit saturation kinetics which are interpreted in terms of reversible formation of Fe(dmpe)2(arene), followed by conversion to Fe(dmpe)2(aryl)H with rate constants of ca. 106 s−1. UV irradiation of Fe(dmpe)2H2 in Ar matrices at 12 K also yields Fe(dmpe)2 (UV and IR detection). The reaction may be partially reversed by selective photolysis. Irradiation in CO- or N2-doped matrices yields Fe(dmpe)2L (L = CO, N2): in a methane matrix the photoproduct is Fe(dmpe)2(CH3)H. Fe(dmpe)2 differs drastically from Ru(dmpe)2 in its absorption spectrum and its reactivity. Most notably, the rate constant for reaction with H2 is a factor of 7500 smaller for Fe(dmpe)2 than for Ru(dmpe)2. In contrast, reactions of both complexes with CO are diffusion-controlled.",

author = "Whittlesey, {Michael K.} and Mawby, {Roger J.} and Robert Osman and Perutz, {Robin N.} and Field, {Leslie D.} and Wilkinson, {Matthew P.} and George, {Michael W.}",

year = "1993",

month = sep,

day = "1",

doi = "10.1021/ja00072a016",

language = "English",

volume = "115",

pages = "8627--8637",

journal = "Journal of the American Chemical Society",

issn = "0002-7863",

publisher = "American Chemical Society",

number = "19",

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TY - JOUR

T1 - Transient and Matrix Photochemistry of Fe(dmpe)2H2 (dmpe = Me2PCH2CH2PMe2)

T2 - Dynamics of C-H and H-H Activation

AU - Whittlesey, Michael K.

AU - Mawby, Roger J.

AU - Osman, Robert

AU - Perutz, Robin N.

AU - Field, Leslie D.

AU - Wilkinson, Matthew P.

AU - George, Michael W.

PY - 1993/9/1

Y1 - 1993/9/1

N2 - The transient photochemistry in solution and low-temperature matrix photochemistry of Fe(dmpe)2H2 (dmpe = Me2PCH2CH2PMe2) are reported; this compound is uniquely effective among first-row transition metal complexes in its ability to activate C-H bonds. Pulsed laser photolysis (308 nm) of alkane solutions of Fe(dmpe)2H2 at ambient temperature generates Fe(dmpe)2 (λmax = 355 nm) within 30 ns. In the absence of added quenchers, the latter decays by reaction with the alkane solvent (in pentane, kobs = 630 s−1 at 297 K, ΔH‡ = 25.0 ± 5.9 kJ mol−1, ΔS‡ = −125 ± 22 J K−1 mol−1). The pseudo-first-order rate constants very with alkane by a factor of ca. 4. Fe(dmpe)2 is quenched by added reagents with second-order rate constants in the range 109-104 dm3 mol−1 s−1, decreasing in the order CO ≫ H2 > C2H4 > N2 > cyclopentene > Et3SiH. The activation parameters for reaction with Et3SiH are ΔH‡ = 22.4 ± 1.8 kJ mol–1, ΔS‡ = −87 ± 6 J K−1 mol−1. The product of reaction with CO is demonstrated by time-resolved IR spectroscopy to be Fe(dmpe)2(CO), which forms at the same rate as the transient decays. The reactions with arenes (benzene and toluene) in cyclohexane exhibit saturation kinetics which are interpreted in terms of reversible formation of Fe(dmpe)2(arene), followed by conversion to Fe(dmpe)2(aryl)H with rate constants of ca. 106 s−1. UV irradiation of Fe(dmpe)2H2 in Ar matrices at 12 K also yields Fe(dmpe)2 (UV and IR detection). The reaction may be partially reversed by selective photolysis. Irradiation in CO- or N2-doped matrices yields Fe(dmpe)2L (L = CO, N2): in a methane matrix the photoproduct is Fe(dmpe)2(CH3)H. Fe(dmpe)2 differs drastically from Ru(dmpe)2 in its absorption spectrum and its reactivity. Most notably, the rate constant for reaction with H2 is a factor of 7500 smaller for Fe(dmpe)2 than for Ru(dmpe)2. In contrast, reactions of both complexes with CO are diffusion-controlled.

AB - The transient photochemistry in solution and low-temperature matrix photochemistry of Fe(dmpe)2H2 (dmpe = Me2PCH2CH2PMe2) are reported; this compound is uniquely effective among first-row transition metal complexes in its ability to activate C-H bonds. Pulsed laser photolysis (308 nm) of alkane solutions of Fe(dmpe)2H2 at ambient temperature generates Fe(dmpe)2 (λmax = 355 nm) within 30 ns. In the absence of added quenchers, the latter decays by reaction with the alkane solvent (in pentane, kobs = 630 s−1 at 297 K, ΔH‡ = 25.0 ± 5.9 kJ mol−1, ΔS‡ = −125 ± 22 J K−1 mol−1). The pseudo-first-order rate constants very with alkane by a factor of ca. 4. Fe(dmpe)2 is quenched by added reagents with second-order rate constants in the range 109-104 dm3 mol−1 s−1, decreasing in the order CO ≫ H2 > C2H4 > N2 > cyclopentene > Et3SiH. The activation parameters for reaction with Et3SiH are ΔH‡ = 22.4 ± 1.8 kJ mol–1, ΔS‡ = −87 ± 6 J K−1 mol−1. The product of reaction with CO is demonstrated by time-resolved IR spectroscopy to be Fe(dmpe)2(CO), which forms at the same rate as the transient decays. The reactions with arenes (benzene and toluene) in cyclohexane exhibit saturation kinetics which are interpreted in terms of reversible formation of Fe(dmpe)2(arene), followed by conversion to Fe(dmpe)2(aryl)H with rate constants of ca. 106 s−1. UV irradiation of Fe(dmpe)2H2 in Ar matrices at 12 K also yields Fe(dmpe)2 (UV and IR detection). The reaction may be partially reversed by selective photolysis. Irradiation in CO- or N2-doped matrices yields Fe(dmpe)2L (L = CO, N2): in a methane matrix the photoproduct is Fe(dmpe)2(CH3)H. Fe(dmpe)2 differs drastically from Ru(dmpe)2 in its absorption spectrum and its reactivity. Most notably, the rate constant for reaction with H2 is a factor of 7500 smaller for Fe(dmpe)2 than for Ru(dmpe)2. In contrast, reactions of both complexes with CO are diffusion-controlled.

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U2 - 10.1021/ja00072a016

DO - 10.1021/ja00072a016

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SN - 0002-7863

VL - 115

SP - 8627

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JO - Journal of the American Chemical Society

JF - Journal of the American Chemical Society

IS - 19

ER -

Transient and Matrix Photochemistry of Fe(dmpe)₂H₂ (dmpe = Me₂PCH₂CH₂PMe₂): Dynamics of C-H and H-H Activation

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