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Ultrafast Chelation Dynamics of Cyclopentadienyl Manganese Tricarbonyl Derivatives with Pendant Sulfides

Published

Author(s)

J S. Yeston, Edwin J. Heilweil, T T. To, Theodore J. Burkey

Abstract

The photoinduced dynamics of two new [h5-C5H4C(O)R]Mn(CO)3 complexes 2 (R = CH(SCH3)2) and 3 (R = C(SCH3)3) have been investigated in n-heptane solution on the ps to us timescale by UV-pump IR-probe transient absorption spectroscopy. Irradiation of 2 at 266 nm or 289 nm induces CO loss to yield two initial products in approximately equal abundance, assigned by their CO-stretching bands to be a heptane solvate of the unsaturated Mn fragment and a ring-formed product in which the pendant sulfide moiety is coordinated to the metal center. In direct analogy with the previously observed behavior of [h5-C5H4C(O)CH2(SCH3)]Mn(CO)3 (1), the solvate reacts through a secondary pathway to afford the S-bound product within 200 ns. Irradiation of 3 under identical conditions yields the chelated product exclusively, with no evidence of a competing solvation pathway.
Citation
Journal of Physical Chemistry Part B Condensed Matter, Materials, Surfaces, Interfaces & Biophysical
Volume
108
Issue
No. 15

Keywords

chelation, ligand rearrangement, metal carbonyl, photochemistry, photoswitch, time-resolved infrared, ultrafast dynamics, vibrational spectroscopy

Citation

Yeston, J. , Heilweil, E. , To, T. and Burkey, T. (2004), Ultrafast Chelation Dynamics of Cyclopentadienyl Manganese Tricarbonyl Derivatives with Pendant Sulfides, Journal of Physical Chemistry Part B Condensed Matter, Materials, Surfaces, Interfaces & Biophysical (Accessed April 16, 2024)
Created March 31, 2004, Updated October 12, 2021