An Unusual Relationship between 49Ti Chemical Shift and Ti(2p3/2) Binding Energy. The Use of 49Ti NMR in Evaluating the Electronic Effect of Methyl Substitution on the Cyclopentadienyl Ligand

Paul G. Gassman, William H. Campbell, David W Macomber

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Abstract

The 49Ti NMR chemical shifts of a series of titanocene derivatives have been shown to have an inverse relationship to the Ti(2P3/2) binding energies of these same compounds as measured by X-ray photoelectron spectroscopy (ESCA). Replacement of one cyclopentadienyl (Cp) group of the titanocene difluorides, dichlorides, and dibromides by a pentamethylcyclopentadienyl (Cp;) moiety resulted in an average downfield shift in the 49Ti NMR absorption of 148 ppm. Substitution of both Cp groups by Cp groups resulted in an average downfield shift of 312 ppm.

Original languageEnglish (US)
Pages (from-to)385-387
Number of pages3
JournalOrganometallics
Volume3
Issue number3
DOIs
StatePublished - Jan 1984

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Chemical shift
Binding energy
chemical equilibrium
Substitution reactions
binding energy
Nuclear magnetic resonance
substitutes
Ligands
nuclear magnetic resonance
ligands
electronics
dibromides
difluorides
X ray photoelectron spectroscopy
shift
dichlorides
Derivatives
photoelectron spectroscopy
titanocene
x rays

Cite this

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title = "An Unusual Relationship between 49Ti Chemical Shift and Ti(2p3/2) Binding Energy. The Use of 49Ti NMR in Evaluating the Electronic Effect of Methyl Substitution on the Cyclopentadienyl Ligand",
abstract = "The 49Ti NMR chemical shifts of a series of titanocene derivatives have been shown to have an inverse relationship to the Ti(2P3/2) binding energies of these same compounds as measured by X-ray photoelectron spectroscopy (ESCA). Replacement of one cyclopentadienyl (Cp) group of the titanocene difluorides, dichlorides, and dibromides by a pentamethylcyclopentadienyl (Cp⋆;) moiety resulted in an average downfield shift in the 49Ti NMR absorption of 148 ppm. Substitution of both Cp groups by Cp⋆ groups resulted in an average downfield shift of 312 ppm.",
author = "Gassman, {Paul G.} and Campbell, {William H.} and Macomber, {David W}",
year = "1984",
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T1 - An Unusual Relationship between 49Ti Chemical Shift and Ti(2p3/2) Binding Energy. The Use of 49Ti NMR in Evaluating the Electronic Effect of Methyl Substitution on the Cyclopentadienyl Ligand

AU - Gassman, Paul G.

AU - Campbell, William H.

AU - Macomber, David W

PY - 1984/1

Y1 - 1984/1

N2 - The 49Ti NMR chemical shifts of a series of titanocene derivatives have been shown to have an inverse relationship to the Ti(2P3/2) binding energies of these same compounds as measured by X-ray photoelectron spectroscopy (ESCA). Replacement of one cyclopentadienyl (Cp) group of the titanocene difluorides, dichlorides, and dibromides by a pentamethylcyclopentadienyl (Cp⋆;) moiety resulted in an average downfield shift in the 49Ti NMR absorption of 148 ppm. Substitution of both Cp groups by Cp⋆ groups resulted in an average downfield shift of 312 ppm.

AB - The 49Ti NMR chemical shifts of a series of titanocene derivatives have been shown to have an inverse relationship to the Ti(2P3/2) binding energies of these same compounds as measured by X-ray photoelectron spectroscopy (ESCA). Replacement of one cyclopentadienyl (Cp) group of the titanocene difluorides, dichlorides, and dibromides by a pentamethylcyclopentadienyl (Cp⋆;) moiety resulted in an average downfield shift in the 49Ti NMR absorption of 148 ppm. Substitution of both Cp groups by Cp⋆ groups resulted in an average downfield shift of 312 ppm.

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