Solution Infrared Spectroscopic Studies on Equilibrium Reactions of CO with the Decamethylmetallocenes Cp*2MII, Where MII = Mg, Ca, Sr, Ba, Sm, Eu, Yb

Selg, Peter, Brintzinger, Hans H., Schultz, Madeleine, & Andersen, Richard A. (2002) Solution Infrared Spectroscopic Studies on Equilibrium Reactions of CO with the Decamethylmetallocenes Cp*2MII, Where MII = Mg, Ca, Sr, Ba, Sm, Eu, Yb. Organometallics, 21(15), pp. 3100-3107.

View at publisher


The reaction of CO with the alkaline-earth decamethylmetallocenes Cp2MII, 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 Cp2MCO is observed to form under CO pressure. The CO stretching frequencies for Cp2CaCO (2158 cm-1), Cp2SrCO (2159 cm-1), Cp2SmCO (2153 cm-1), and Cp2EuCO (2150 cm-1) are greater than that of free CO (2134 cm-1 in toluene or methylcyclohexane). In contrast, Cp2YbCO has nuCO 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 Cp2Yb(CO)2 with an even lower nuCO value of 2072 cm-1 predominates. Equilibrium constants were determined as a function of pressure and temperature for the equilibria Cp2MII(solv) + nCO(gas or solv) Cp2MII(CO)n(solv), with MII = Ca, Eu, Yb. The thermodynamic constants delta H degrees, delta S degrees, and delta G degrees for the formation of each species, extracted from the changes in the intensity of the corresponding iotaR absorption bands, indicate weak MII-CO binding. Models to account for the bonding in these metallocene CO adducts are discussed.

Impact and interest:

26 citations in Scopus
19 citations in Web of Science®
Search Google Scholar™

Citation counts are sourced monthly from Scopus and Web of Science® citation databases.

These databases contain citations from different subsets of available publications and different time periods and thus the citation count from each is usually different. Some works are not in either database and no count is displayed. Scopus includes citations from articles published in 1996 onwards, and Web of Science® generally from 1980 onwards.

Citations counts from the Google Scholar™ indexing service can be viewed at the linked Google Scholar™ search.

ID Code: 9088
Item Type: Journal Article
Refereed: Yes
Additional Information: This article is freely available from the American Chemical Society website 12 months after the publication date. See links to publisher website in this record.
DOI: 10.1021/om011045r
ISSN: 1520-6041
Subjects: Australian and New Zealand Standard Research Classification > CHEMICAL SCIENCE (030000) > OTHER CHEMICAL SCIENCES (039900) > Organometallic Chemistry (039904)
Divisions: Past > QUT Faculties & Divisions > Faculty of Science and Technology
Copyright Owner: Copyright 2002 American Chemical Society
Deposited On: 20 Aug 2007 00:00
Last Modified: 09 Mar 2011 01:58

Export: EndNote | Dublin Core | BibTeX

Repository Staff Only: item control page