Computational, spectroscopic, and crystallographic determination of the molecular structures of CO adducts of Vaska-type complexes trans-IrL2(CO)2X

Faraj Abu-Hasanayn; Thomas J. Emge; John A. Maguire; Karsten Krogh-Jespersen; Alan S Goldman

Computational, spectroscopic, and crystallographic determination of the molecular structures of CO adducts of Vaska-type complexes trans-IrL₂(CO)₂X

Faraj Abu-Hasanayn, Thomas J. Emge, John A. Maguire, Karsten Krogh-Jespersen, Alan S Goldman

Rutgers University

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8 Citations (Scopus)

Abstract

The products of CO addition to Vaska-type complexes, trans-Ir(PH₃)₂(CO)₂X (X = Cl, I), have been calculated by use of ab initio electronic structure methods with effective core potentials on all non-hydrogen atoms and basis sets of double-ζ plus polarization function quality. The calculated trigonal-bipyramidal structure of Ir(PH₃)₂(CO)₂Cl differs significantly from the results of a previous crystallographic structure determination of Ir(PPh₃)₂(CO)₂Cl for which significant disorder and crystal decomposition during data collection were reported. In particular, the calculated OC-Ir-CO angle (133-138°) is significantly greater than the reported crystallographic value (121°). Results of a crystallographic (X - I, 131°) and IR spectroscopic (X = Cl, 132°; I, 133°) reinvestigation are in good agreement with the calculations. The origin of the distortion from idealized trigonal-bipyramidal geometry is briefly discussed.

Original language	English
Pages (from-to)	5177-5180
Number of pages	4
Journal	Organometallics
Volume	13
Issue number	12
Publication status	Published - 1994

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ASJC Scopus subject areas

Inorganic Chemistry
Organic Chemistry

Cite this

Abu-Hasanayn, F., Emge, T. J., Maguire, J. A., Krogh-Jespersen, K., & Goldman, A. S. (1994). Computational, spectroscopic, and crystallographic determination of the molecular structures of CO adducts of Vaska-type complexes trans-IrL₂(CO)₂X. Organometallics, 13(12), 5177-5180.

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title = "Computational, spectroscopic, and crystallographic determination of the molecular structures of CO adducts of Vaska-type complexes trans-IrL2(CO)2X",

abstract = "The products of CO addition to Vaska-type complexes, trans-Ir(PH3)2(CO)2X (X = Cl, I), have been calculated by use of ab initio electronic structure methods with effective core potentials on all non-hydrogen atoms and basis sets of double-ζ plus polarization function quality. The calculated trigonal-bipyramidal structure of Ir(PH3)2(CO)2Cl differs significantly from the results of a previous crystallographic structure determination of Ir(PPh3)2(CO)2Cl for which significant disorder and crystal decomposition during data collection were reported. In particular, the calculated OC-Ir-CO angle (133-138°) is significantly greater than the reported crystallographic value (121°). Results of a crystallographic (X - I, 131°) and IR spectroscopic (X = Cl, 132°; I, 133°) reinvestigation are in good agreement with the calculations. The origin of the distortion from idealized trigonal-bipyramidal geometry is briefly discussed.",

author = "Faraj Abu-Hasanayn and Emge, {Thomas J.} and Maguire, {John A.} and Karsten Krogh-Jespersen and Goldman, {Alan S}",

year = "1994",

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T1 - Computational, spectroscopic, and crystallographic determination of the molecular structures of CO adducts of Vaska-type complexes trans-IrL2(CO)2X

AU - Abu-Hasanayn, Faraj

AU - Emge, Thomas J.

AU - Maguire, John A.

AU - Krogh-Jespersen, Karsten

AU - Goldman, Alan S

PY - 1994

Y1 - 1994

N2 - The products of CO addition to Vaska-type complexes, trans-Ir(PH3)2(CO)2X (X = Cl, I), have been calculated by use of ab initio electronic structure methods with effective core potentials on all non-hydrogen atoms and basis sets of double-ζ plus polarization function quality. The calculated trigonal-bipyramidal structure of Ir(PH3)2(CO)2Cl differs significantly from the results of a previous crystallographic structure determination of Ir(PPh3)2(CO)2Cl for which significant disorder and crystal decomposition during data collection were reported. In particular, the calculated OC-Ir-CO angle (133-138°) is significantly greater than the reported crystallographic value (121°). Results of a crystallographic (X - I, 131°) and IR spectroscopic (X = Cl, 132°; I, 133°) reinvestigation are in good agreement with the calculations. The origin of the distortion from idealized trigonal-bipyramidal geometry is briefly discussed.

AB - The products of CO addition to Vaska-type complexes, trans-Ir(PH3)2(CO)2X (X = Cl, I), have been calculated by use of ab initio electronic structure methods with effective core potentials on all non-hydrogen atoms and basis sets of double-ζ plus polarization function quality. The calculated trigonal-bipyramidal structure of Ir(PH3)2(CO)2Cl differs significantly from the results of a previous crystallographic structure determination of Ir(PPh3)2(CO)2Cl for which significant disorder and crystal decomposition during data collection were reported. In particular, the calculated OC-Ir-CO angle (133-138°) is significantly greater than the reported crystallographic value (121°). Results of a crystallographic (X - I, 131°) and IR spectroscopic (X = Cl, 132°; I, 133°) reinvestigation are in good agreement with the calculations. The origin of the distortion from idealized trigonal-bipyramidal geometry is briefly discussed.

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