ChemInform Abstract: The Photochemistry of Cyclopentadienyl Platinum Carbonyl Dimers: Characterization of (Pt2(μ-CO)(η5-C5R5)2) (R: H or Me) Using Matrix Isolation and Fast Time-Resolved Infrared Spectroscopy.

We have used fast Time-resolved Infrared Spectroscopy (TRIR) to probe organometallic reactions in supercritical fluids on the nanosecond time-scale. This has allowed us to identify, for the first time in solution at room temperature, organometallic noble gas complexes which are formed following irradiation of metal carbonyls in supercritical noble gas solution. We have found that these complexes are surprisingly stable and have comparable reactivity to organometallic alkane complexes. We have also studied the coordination of CO2 to metal centres in supercritical CO2 (scCO2) and provide the first evidence for the formation and reactivity of ɳ1-O bound metal CO2 complexes in solution at or above room temperature.

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Fast time-resolved infrared spectroscopy of organometallic intermediates; detection of [(η5-C5H5)Fe(CO)2] and [(η5-C5H5)Fe(µ-CO)3Fe(η5-C5H5)] in room-temperature solution

Journal of the Chemical Society Chemical Communications ◽

10.1039/c39840000972 ◽

1984 ◽

pp. 972-974 ◽

Cited By ~ 48

Author(s):

Barry D. Moore ◽

Michael B. Simpson ◽

Martyn Poliakoff ◽

James J. Turner

Keyword(s):

Infrared Spectroscopy ◽

Room Temperature ◽

Fast Time ◽

Time Resolved ◽

Temperature Solution ◽

Time Resolved Infrared Spectroscopy

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Excited States and Intermediates by Time-Resolved Infrared Spectroscopy

Laser Chemistry ◽

10.1155/1999/31863 ◽

1999 ◽

Vol 19 (1-4) ◽

pp. 245-251 ◽

Cited By ~ 4

Author(s):

J. J. Turner ◽

M. W. George ◽

I. P. Clark ◽

I. G. Virrels

Keyword(s):

Infrared Spectroscopy ◽

Excited State ◽

Charge Transfer ◽

Excited States ◽

Fast Time ◽

Time Resolved ◽

Excited Species ◽

Charge Transfer Transitions ◽

Time Resolved Infrared Spectroscopy ◽

Kinetics Of

For coordination compounds containing CO or CN groups, fast time-resolved infrared spectroscopy (TRIR) provides a convenient method of probing excited states and intermediates. TRIR has proved particularly powerful for probing the structure and kinetics of organometallic intermediates. The interpretation is particularly straightforward when combined with IR data from matrix isolation experiments, although there can be some subtle differences. In excited state studies, shifts in ν(CO) and ν(CN) frequencies, from ground to excited state, are sensitive to the changes in electron distribution on excitation, thus allowing the distinction between charge-transfer and non-charge-transfer transitions. Subtle effects on excited state ν(CO) band positions occur with change from fluid to rigid solvent-“infrared rigidochromism”. There is often a change in ν(CO) band width on excitation; this can be interpreted in terms of specific interactions between the excited species and the solvent. This paper presents some of our recent work in this area.

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