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Solution infrared spectroscopic studies on equilibrium reactions of CO with the decamethylmetallocenes Cp*2MII, where MII = Mg, Ca, Sr, Ba, Sm, Eu, Yb

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2002

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Selg, Peter
Schultz, Madeleine
Andersen, Richard A.

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Organometallics. 2002, 21(15), pp. 3100-3107. ISSN 0276-7333. eISSN 1520-6041. Available under: doi: 10.1021/om011045r

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The reaction of CO with the alkaline-earth decamethylmetallocenes Cp*2MII, where MII is Mg, Ca, Sr, or Ba, and the bivalent lanthanide decamethylmetallocenes, where MII is Sm, Eu, or Yb, have been studied in toluene or methylcyclohexane solution in a high-pressure infrared cell. In all cases, except for Mg and Ba, the monocarbonyl complex Cp*2MCO is observed to form under CO pressure. The CO stretching frequencies for Cp*2CaCO (2158 cm-1), Cp*2SrCO (2159 cm-1), Cp*2SmCO (2153 cm-1), and Cp*2EuCO (2150 cm-1) are greater than that of free CO (2134 cm-1 in toluene or methylcyclohexane). In contrast, Cp*2YbCO has νCO 2114 cm-1, below that of free CO. This 1:1 complex is formed at low CO pressure (<2 bar); at higher CO pressures the 1:2 adduct Cp*2Yb(CO)2 with an even lower νCO value of 2072 cm-1 predominates. Equilibrium constants were determined as a function of pressure and temperature for the equilibria Cp*2MII(solv) + nCO(gas or solv) Cp*2MII(CO)n(solv), with MII = Ca, Eu, Yb. The thermodynamic constants ΔH°, ΔS°, and ΔG° for the formation of each species, extracted from the changes in the intensity of the corresponding ΙR absorption bands, indicate weak MII−CO binding. Models to account for the bonding in these metallocene CO adducts are discussed.

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ISO 690SELG, Peter, Hans-Herbert BRINTZINGER, Madeleine SCHULTZ, Richard A. ANDERSEN, 2002. Solution infrared spectroscopic studies on equilibrium reactions of CO with the decamethylmetallocenes Cp*2MII, where MII = Mg, Ca, Sr, Ba, Sm, Eu, Yb. In: Organometallics. 2002, 21(15), pp. 3100-3107. ISSN 0276-7333. eISSN 1520-6041. Available under: doi: 10.1021/om011045r
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@article{Selg2002Solut-23728,
  year={2002},
  doi={10.1021/om011045r},
  title={Solution infrared spectroscopic studies on equilibrium reactions of CO with the decamethylmetallocenes Cp*<sub>2</sub>M<sup>II</sup>, where M<sup>II</sup> = Mg, Ca, Sr, Ba, Sm, Eu, Yb},
  number={15},
  volume={21},
  issn={0276-7333},
  journal={Organometallics},
  pages={3100--3107},
  author={Selg, Peter and Brintzinger, Hans-Herbert and Schultz, Madeleine and Andersen, Richard A.}
}
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    <dcterms:title>Solution infrared spectroscopic studies on equilibrium reactions of CO with the decamethylmetallocenes Cp*&lt;sub&gt;2&lt;/sub&gt;M&lt;sup&gt;II&lt;/sup&gt;, where M&lt;sup&gt;II&lt;/sup&gt; = Mg, Ca, Sr, Ba, Sm, Eu, Yb</dcterms:title>
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    <dcterms:abstract xml:lang="eng">The reaction of CO with the alkaline-earth decamethylmetallocenes Cp*&lt;sub&gt;2&lt;/sub&gt;M&lt;sup&gt;II&lt;/sup&gt;, where M&lt;sup&gt;II&lt;/sup&gt; is Mg, Ca, Sr, or Ba, and the bivalent lanthanide decamethylmetallocenes, where M&lt;sup&gt;II&lt;/sup&gt; is Sm, Eu, or Yb, have been studied in toluene or methylcyclohexane solution in a high-pressure infrared cell. In all cases, except for Mg and Ba, the monocarbonyl complex Cp*&lt;sub&gt;2&lt;/sub&gt;MCO is observed to form under CO pressure. The CO stretching frequencies for Cp*&lt;sub&gt;2&lt;/sub&gt;CaCO (2158 cm&lt;sup&gt;-1&lt;/sup&gt;), Cp*&lt;sub&gt;2&lt;/sub&gt;SrCO (2159 cm&lt;sup&gt;-1&lt;/sup&gt;), Cp*&lt;sub&gt;2&lt;/sub&gt;SmCO (2153 cm&lt;sup&gt;-1&lt;/sup&gt;), and Cp*&lt;sub&gt;2&lt;/sub&gt;EuCO (2150 cm&lt;sup&gt;-1&lt;/sup&gt;) are greater than that of free CO (2134 cm&lt;sup&gt;-1&lt;/sup&gt; in toluene or methylcyclohexane). In contrast, Cp*&lt;sub&gt;2&lt;/sub&gt;YbCO has νCO 2114 cm&lt;sup&gt;-1&lt;/sup&gt;, below that of free CO. This 1:1 complex is formed at low CO pressure (&lt;2 bar); at higher CO pressures the 1:2 adduct Cp*&lt;sub&gt;2&lt;/sub&gt;Yb(CO)&lt;sub&gt;2&lt;/sub&gt; with an even lower νCO value of 2072 cm&lt;sup&gt;-1&lt;/sup&gt; predominates. Equilibrium constants were determined as a function of pressure and temperature for the equilibria Cp*&lt;sub&gt;2&lt;/sub&gt;M&lt;sup&gt;II&lt;/sup&gt;(solv) + nCO(gas or solv) Cp*&lt;sub&gt;2&lt;/sub&gt;M&lt;sup&gt;II&lt;/sup&gt;(CO)&lt;sub&gt;n&lt;/sub&gt;(solv), with M&lt;sup&gt;II&lt;/sup&gt; = Ca, Eu, Yb. The thermodynamic constants ΔH°, ΔS°, and ΔG° for the formation of each species, extracted from the changes in the intensity of the corresponding ΙR absorption bands, indicate weak M&lt;sup&gt;II&lt;/sup&gt;−CO binding. Models to account for the bonding in these metallocene CO adducts are discussed.</dcterms:abstract>
    <dc:contributor>Schultz, Madeleine</dc:contributor>
    <dc:contributor>Brintzinger, Hans-Herbert</dc:contributor>
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