ACS - PRF1 MICROWAVE STRUCTURE MEASUREMENTS  Microwave spectroscopy measurements have yielded the first accurate gas- phase structural parameters for.

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ACS - PRF1 MICROWAVE STRUCTURE MEASUREMENTS  Microwave spectroscopy measurements have yielded the first accurate gas- phase structural parameters for Os(CO) 4 (  2 -C 2 H 4 ), tetracarbonylethyleneosmium[i].[i]  The deformation of the ethylene ligand upon coordination to osmium is large, well-determined and supports the DCD model. The new experimental ethylene C—C bond length of 1.43 Å for the complex falls between the free ethylene average r z (C=C) value of 1.339(1) Å and the r 0 (C—C) bond length of 1.534(2) Å for ethane. The C—C bond length for the Fe congener is 1.421(7) Å.  The angle between the plane of the CH 2 group and the C—C bond (  out-of- plane) is 26°. This angle is 22° for Fe(CO) 4 (C 2 H 4 ), indicating that the degree of metal (d  )  olefin (  *) back-bonding is greater for the Os complex.  A homodyne-type detection system, was developed for our pulsed-beam Fourier transform spectrometer system and used for these measurements. This homodyne system greatly simplifies the microwave circuit, with no apparent loss in sensitivity. [i] C. Karunatilaka, B. S. Tackett, J. Washington, and S. G. Kukolich, J. Am. Chem. Soc. 129(34), (2007) (doi: /ja S (07) ).[i]

ACS - PRF2 Ethylene Structure Changes on Complex Formation

ACS - PRF3 DCD Model for Alkene-Metal Complexes  Model to describe alkene bonding to a transition metal, proposed by Dewar[1] over 50 years ago.[1]  Model was successfully applied by Chatt and Duncanson[2] for a systematic description of metal-olefin complexes and is now termed the DCD model.[2]  Dewar[3] suggested the existence of two extremes of the metal-olefin bonding, from “simple  -complex” to metallacyclopropane, like classical, strained three- membered ring. Metal-olefin bonds fall somewhere between. ______________________________________________[3] [ 1][ 1] Dewar, M. J. S. Bull. Soc. Chim. Fr. 1951, 18, C71. [2][2] Chatt, J; Duncanson, L. A. J. Chem. Soc. 1953, [3][3] Dewar, M. J. S.; Ford, G. P. J. Am. Chem. Soc. 1979, 101(4), 783.

ACS - PRF4 Homodyne system greatly simplifies the microwave circuit, with no apparent loss in sensitivity[1] Rest of F-T spectrometer is similar to earlier spectrometers.[2][1][2] [1][1] Tackett, B. S.; Karunatilaka, C.; Daly, A.; Kukolich, S. G. Organometallics 2007, 26, [2][2].Bumgarner, R. E.; Kukolich, S. G. J. Chem. Phys. 1987, 86(3),

ACS - PRF5 Acknowledgements ACS-PRF - Acknowledgement is made to the Donors of The American Chemical Society Petroleum Research Fund, for the partial support of this research. N$F - This material is based upon work supported by the National Science Foundation under Grant No. CHE Giles L. Henderson and Richard Keiter of Eastern Illinois University started this spectroscopy project in 1992