The photochemistry of (η3-2-R-C3H4)Fe(CO)(NO)(X) (R=H or Cl; X=CO or PPh3) in room temperature solution or frozen gas matrixes

Long, Conor; Maher, Kieran; Pryce, Mary T.

doi:10.1016/j.jorganchem.2006.04.004

Cited by 6 publications

(6 citation statements)

References 15 publications

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“…The MI apparatus has been described in detail elsewhere. 26 Infrared spectra were recorded using a Perkin Elmer Spectrum One Fourier-transform spectrophotometer operating at 1 cm −1 resolution and acquiring 16 scans per spectrum. The psTRIR apparatus used UV pump and mid-IR probe pulses generated by a Ti:sapphire laser with a repetition rate of 1 kHz.…”

Section: Methodsmentioning

confidence: 99%

An investigation into the photochemistry of, and the electrochemically induced CO-loss from, [(CO)₅MC(OMe)Me](M = Cr or W) using low-temperature matrix isolation, picosecond infrared spectroscopy, cyclic voltammetry, and time-dependent density functional theory

et al. 2015

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propanone singlet excited state was detected on the reaction path to the metallaketene species. This metallacyclopropanone excited state species has a lifetime of less than 100 ps and a characteristic bridging carbonyl band at 1770 cm −1 . The tungsten ketene species was also detected but in contrast to the chromium system, this forms directly from a low-lying triplet excited state. The electrochemical release of CO showed a greater efficiency for the chromium complex when compared to the tungsten.

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Section: Methodsmentioning

confidence: 99%

An investigation into the photochemistry of, and the electrochemically induced CO-loss from, [(CO)₅MC(OMe)Me](M = Cr or W) using low-temperature matrix isolation, picosecond infrared spectroscopy, cyclic voltammetry, and time-dependent density functional theory

et al. 2015

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“…The matrix isolation apparatus has been described in detail elsewhere . It consists of a HC2 closed helium displex refrigerator supplied by APD Cryogenics in thermal contact with a CaF 2 optical flat, contained within a stainless steel shroud equipped with CaF 2 windows.…”

Section: Methodsmentioning

confidence: 99%

“…The matrix isolation apparatus has been described in detail elsewhere. 35 It consists of a HC2 closed helium displex refrigerator supplied by APD Cryogenics in thermal contact with a CaF 2 optical flat, contained within a stainless steel shroud equipped with CaF 2 windows. The temperature of the matrix was maintained by a heating current controlled by a Lakeshore 330 analog temperature control unit The optical flat was capable of rotation through 90°, allowing it to alternatively face the sample vapor/isolating gas streams and the monitoring spectrophotometers.…”

Section: Methodsmentioning

confidence: 99%

Unusually Slow Photodissociation of CO from (η⁶-C₆H₆)Cr(CO)₃ (M = Cr or Mo): A Time-Resolved Infrared, Matrix Isolation, and DFT Investigation

et al. 2009

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The photochemistry of (η6-C6H6)M(CO)3 (M = Cr or Mo) is described. Photolysis with λexc. > 300 nm of (η6-C6H6)Cr(CO)3 in low-temperature matrixes containing CO produced the CO-loss product, while lower energy photolysis (λexc. > 400 nm) produced Cr(CO)6. Pulsed photolysis (λexc. = 400 nm) of (η6-C6H6)Cr(CO)3 in n-heptane solution at room temperature produced an excited-state species (1966 and 1888 cm−1) that decays over 150 ps to (η6-C6H6)Cr(CO)2(n-heptane) (70%) and (η6-C6H6)Cr(CO)3 (30%). Pulsed photolysis (λexc. = 266 nm) of (η6-C6H6)Cr(CO)3 in n-heptane produced bands assigned to (η6-C6H6)Cr(CO)2(n-heptane) (1930 and 1870 cm−1) within 1 ps. These bands increase with a rate identical to the rate of decay of the excited-state species and the rate of recovery of (η6-C6H6)Cr(CO)3. Photolysis of (η6-C6H6)Mo(CO)3 at 400 nm produced an excited-state species (1996 and 1898 cm−1) and traces of (η6-C6H6)Mo(CO)2(n-heptane) within 1 ps. For the chromium system CO-loss can occur following excitation at both 400 and 266 nm via an avoided crossing of a MACT (metal-to-arene charge transfer) and MCCT/LF (metal-to-carbonyl charge transfer/ligand field) states. This leads to an unusually slow CO-loss following excitation with 400 nm light. Rapid CO-loss is observed following 266 nm excitation because of direct population of the MCCT/LF state. The quantum yield for CO-loss in the chromium system decreases with increasing excitation energy because of the competing population of a high-energy unreactive MACT state. For the molydenum system CO-loss is a minor process for 400 nm excitation, and an unreactive MACT state is evident from the TRIR spectra. A higher quantum yield for CO-loss is observed following 266 nm excitation through both direct population of the MCCT/LF state and production of a vibrationally excited reactive MACT state. This results in the quantum yield for CO-loss increasing with increasing excitation energy.

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“…The Matrix isolation apparatus has been described in elsewhere [49]. Briefly the matrix isolation apparatus consists of a closed cycle helium refrigerator, sample window, shroud, deposition tube, gas mixing chamber, gas inlet, backing pump, diffusion pump and temperature control unit.…”

Section: Matrix Isolationmentioning

confidence: 99%

Matrix effects and their role in the low-temperature photochemistry of (η-Aniline)Cr(CO)3

Alamiry

Long

Fidgeon

et al. 2010

Journal of Organometallic Chemistry

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The photochemistry of (η3-2-R-C3H4)Fe(CO)(NO)(X) (R=H or Cl; X=CO or PPh3) in room temperature solution or frozen gas matrixes

Cited by 6 publications

References 15 publications

An investigation into the photochemistry of, and the electrochemically induced CO-loss from, [(CO)₅MC(OMe)Me](M = Cr or W) using low-temperature matrix isolation, picosecond infrared spectroscopy, cyclic voltammetry, and time-dependent density functional theory

An investigation into the photochemistry of, and the electrochemically induced CO-loss from, [(CO)₅MC(OMe)Me](M = Cr or W) using low-temperature matrix isolation, picosecond infrared spectroscopy, cyclic voltammetry, and time-dependent density functional theory

Unusually Slow Photodissociation of CO from (η⁶-C₆H₆)Cr(CO)₃ (M = Cr or Mo): A Time-Resolved Infrared, Matrix Isolation, and DFT Investigation

Matrix effects and their role in the low-temperature photochemistry of (η-Aniline)Cr(CO)3

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The photochemistry of (η3-2-R-C3H4)Fe(CO)(NO)(X) (R=H or Cl; X=CO or PPh3) in room temperature solution or frozen gas matrixes

Cited by 6 publications

References 15 publications

An investigation into the photochemistry of, and the electrochemically induced CO-loss from, [(CO)5MC(OMe)Me](M = Cr or W) using low-temperature matrix isolation, picosecond infrared spectroscopy, cyclic voltammetry, and time-dependent density functional theory

An investigation into the photochemistry of, and the electrochemically induced CO-loss from, [(CO)5MC(OMe)Me](M = Cr or W) using low-temperature matrix isolation, picosecond infrared spectroscopy, cyclic voltammetry, and time-dependent density functional theory

Unusually Slow Photodissociation of CO from (η6-C6H6)Cr(CO)3 (M = Cr or Mo): A Time-Resolved Infrared, Matrix Isolation, and DFT Investigation

Matrix effects and their role in the low-temperature photochemistry of (η-Aniline)Cr(CO)3

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An investigation into the photochemistry of, and the electrochemically induced CO-loss from, [(CO)₅MC(OMe)Me](M = Cr or W) using low-temperature matrix isolation, picosecond infrared spectroscopy, cyclic voltammetry, and time-dependent density functional theory

An investigation into the photochemistry of, and the electrochemically induced CO-loss from, [(CO)₅MC(OMe)Me](M = Cr or W) using low-temperature matrix isolation, picosecond infrared spectroscopy, cyclic voltammetry, and time-dependent density functional theory

Unusually Slow Photodissociation of CO from (η⁶-C₆H₆)Cr(CO)₃ (M = Cr or Mo): A Time-Resolved Infrared, Matrix Isolation, and DFT Investigation