Low-temperature-matrix and room-temperature-solution photochemistry of Ru(CO)3(dmpe) (dmpe = Me2PCH2CH2PMe2)

Michael K. Whittlesey; Robin N. Perutz; Ian G. Virrels; Michael W. George

doi:10.1021/om960683k

Low-temperature-matrix and room-temperature-solution photochemistry of Ru(CO)₃(dmpe) (dmpe = Me₂PCH₂CH₂PMe₂)

Michael K. Whittlesey, Robin N. Perutz, Ian G. Virrels, Michael W. George

Research output: Journal Publication › Article › peer-review

23 Citations (Scopus)

Abstract

The photochemistry of Ru(CO)₃(dmpe) (II; dmpe = Me₂PCH₂CH₂PMe₂), has been studied by matrix isolation at 12 K and laser flash photolysis with UV - visible and IR detection at ambient temperature. UV photolysis in a matrix results in the formation of Ru(CO)₂(dmpe)·S (S = matrix host), which shows two distinctive UV-visible bands with λ_max dependent on S (Ar, 410, 600 nm; CH₄, 357, 500 nm; Xe, 345, 457 nm). These shifts are the largest yet observed for any matrix-solvated species. The reactions are partially reversed by long-wavelength (λ > 420 nm) photolysis. Laser flash photolysis in heptane solution (λ_exe = 266 or 308 nm) with IR or UV - visible detection reveals that Ru(CO)₂(dmpe)·heptane is a short-lived fragment which decays rapidly by reaction with Ru(CO)₃(dmpe) (k₂ ≈ 1 × 10⁹ dm³ mol^-1 s^-1). Steady-state photolysis of II in heptane in the presence of hydrogen or triethylsilane yields Ru(CO)₂(dmpe)H₂ and Ru(CO)₂(dmpe)(SiEt3)H, respectively, which have been characterized by IR and NMR spectroscopy.

Original language	English
Pages (from-to)	268-274
Number of pages	7
Journal	Organometallics
Volume	16
Issue number	2
DOIs	https://doi.org/10.1021/om960683k
Publication status	Published - 21 Jan 1997
Externally published	Yes

ASJC Scopus subject areas

Physical and Theoretical Chemistry
Organic Chemistry
Inorganic Chemistry

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title = "Low-temperature-matrix and room-temperature-solution photochemistry of Ru(CO)3(dmpe) (dmpe = Me2PCH2CH2PMe2)",

abstract = "The photochemistry of Ru(CO)3(dmpe) (II; dmpe = Me2PCH2CH2PMe2), has been studied by matrix isolation at 12 K and laser flash photolysis with UV - visible and IR detection at ambient temperature. UV photolysis in a matrix results in the formation of Ru(CO)2(dmpe)·S (S = matrix host), which shows two distinctive UV-visible bands with λmax dependent on S (Ar, 410, 600 nm; CH4, 357, 500 nm; Xe, 345, 457 nm). These shifts are the largest yet observed for any matrix-solvated species. The reactions are partially reversed by long-wavelength (λ > 420 nm) photolysis. Laser flash photolysis in heptane solution (λexe = 266 or 308 nm) with IR or UV - visible detection reveals that Ru(CO)2(dmpe)·heptane is a short-lived fragment which decays rapidly by reaction with Ru(CO)3(dmpe) (k2 ≈ 1 × 109 dm3 mol-1 s-1). Steady-state photolysis of II in heptane in the presence of hydrogen or triethylsilane yields Ru(CO)2(dmpe)H2 and Ru(CO)2(dmpe)(SiEt3)H, respectively, which have been characterized by IR and NMR spectroscopy.",

author = "Whittlesey, {Michael K.} and Perutz, {Robin N.} and Virrels, {Ian G.} and George, {Michael W.}",

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AU - Whittlesey, Michael K.

AU - Perutz, Robin N.

AU - Virrels, Ian G.

AU - George, Michael W.

PY - 1997/1/21

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N2 - The photochemistry of Ru(CO)3(dmpe) (II; dmpe = Me2PCH2CH2PMe2), has been studied by matrix isolation at 12 K and laser flash photolysis with UV - visible and IR detection at ambient temperature. UV photolysis in a matrix results in the formation of Ru(CO)2(dmpe)·S (S = matrix host), which shows two distinctive UV-visible bands with λmax dependent on S (Ar, 410, 600 nm; CH4, 357, 500 nm; Xe, 345, 457 nm). These shifts are the largest yet observed for any matrix-solvated species. The reactions are partially reversed by long-wavelength (λ > 420 nm) photolysis. Laser flash photolysis in heptane solution (λexe = 266 or 308 nm) with IR or UV - visible detection reveals that Ru(CO)2(dmpe)·heptane is a short-lived fragment which decays rapidly by reaction with Ru(CO)3(dmpe) (k2 ≈ 1 × 109 dm3 mol-1 s-1). Steady-state photolysis of II in heptane in the presence of hydrogen or triethylsilane yields Ru(CO)2(dmpe)H2 and Ru(CO)2(dmpe)(SiEt3)H, respectively, which have been characterized by IR and NMR spectroscopy.

AB - The photochemistry of Ru(CO)3(dmpe) (II; dmpe = Me2PCH2CH2PMe2), has been studied by matrix isolation at 12 K and laser flash photolysis with UV - visible and IR detection at ambient temperature. UV photolysis in a matrix results in the formation of Ru(CO)2(dmpe)·S (S = matrix host), which shows two distinctive UV-visible bands with λmax dependent on S (Ar, 410, 600 nm; CH4, 357, 500 nm; Xe, 345, 457 nm). These shifts are the largest yet observed for any matrix-solvated species. The reactions are partially reversed by long-wavelength (λ > 420 nm) photolysis. Laser flash photolysis in heptane solution (λexe = 266 or 308 nm) with IR or UV - visible detection reveals that Ru(CO)2(dmpe)·heptane is a short-lived fragment which decays rapidly by reaction with Ru(CO)3(dmpe) (k2 ≈ 1 × 109 dm3 mol-1 s-1). Steady-state photolysis of II in heptane in the presence of hydrogen or triethylsilane yields Ru(CO)2(dmpe)H2 and Ru(CO)2(dmpe)(SiEt3)H, respectively, which have been characterized by IR and NMR spectroscopy.

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Low-temperature-matrix and room-temperature-solution photochemistry of Ru(CO)₃(dmpe) (dmpe = Me₂PCH₂CH₂PMe₂)

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