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Carbon-13 nuclear magnetic resonance spectra and mechanism of bridge–terminal carbonyl exchange in di-µ-carbonyl-bis[carbonyl(η-cyclopentadienyl)iron](Fe–Fe)[{(η-C5H5)Fe(CO)2}2]; cd-di-µ-carbonyl-f-carbonyl-ae-di(η-cyclopentadienyl)-b-(triethyl -phosphite)di-iron(Fe–Fe)[(η-C5H5)2Fe2(CO)3P(OEt)3], and some related complexes

Harris, Daniel C. and Rosenberg, Edward and Roberts, John D. (1974) Carbon-13 nuclear magnetic resonance spectra and mechanism of bridge–terminal carbonyl exchange in di-µ-carbonyl-bis[carbonyl(η-cyclopentadienyl)iron](Fe–Fe)[{(η-C5H5)Fe(CO)2}2]; cd-di-µ-carbonyl-f-carbonyl-ae-di(η-cyclopentadienyl)-b-(triethyl -phosphite)di-iron(Fe–Fe)[(η-C5H5)2Fe2(CO)3P(OEt)3], and some related complexes. Journal of the Chemical Society. Dalton Transactions, 1974 (22). pp. 2398-2403. ISSN 0300-9246. http://resolver.caltech.edu/CaltechAUTHORS:HARjcsdt74

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Abstract

A mechanism involving carbonyl-bridge breaking, rotation about the Fe–Fe bond, and bridge reformation is shown to account qualitatively for changes in the carbonyl region of the 13C n.m.r spectrum of the complex [(cp)(OC)[graphic omitted]e(cp){P(OEt)3}] and quantitatively for [(cp)(OC)[graphic omitted]e(CO)(cp)](cp =η-cyclopentadienyl).The activation energy for this process, 49.0 ± 4 kJ mol^–1(11.7 ± 1 kcal mol^–1), is close to that reported for cis–trans-isomerization of the cp groups, in accord with this mechanism. Variable-temperature 13C n.m.r. spectra of the complexes [(cp)(OC)[graphic omitted]u(CO)(cp)] and [(cp)(OC)[graphic omitted]i(cp)] are also reported.


Item Type:Article
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http://dx.doi.org/10.1039/DT9740002398DOIUNSPECIFIED
Additional Information:© Royal Society of Chemistry 1974. Received, 8th January, 1974. We thank the National Science Foundation and the Public Health Service for support.
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National Science FoundationUNSPECIFIED
Public Health ServiceUNSPECIFIED
Record Number:CaltechAUTHORS:HARjcsdt74
Persistent URL:http://resolver.caltech.edu/CaltechAUTHORS:HARjcsdt74
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ID Code:12272
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Deposited On:31 Oct 2008 18:45
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