Carbonyl cyclopentadienylnitro complexes of iron and ruthenium and their oxygen atom transfer reactions.

Persistent Link:
http://hdl.handle.net/10150/184482
Title:
Carbonyl cyclopentadienylnitro complexes of iron and ruthenium and their oxygen atom transfer reactions.
Author:
Hansen, Craig Allen.
Issue Date:
1988
Publisher:
The University of Arizona.
Rights:
Copyright © is held by the author. Digital access to this material is made possible by the University Libraries, University of Arizona. Further transmission, reproduction or presentation (such as public display or performance) of protected items is prohibited except with permission of the author.
Abstract:
New and reactive nitro organometallics, Fe(C₅H₅)(CO)₂(NO₂), Ru(C₅H₅)(CO)₂(NO₂), their nitrogen-15 derivatives, Fe(C₅H₅)(CO)(PPh₃)(NO₂), and [Fe(C₅H₅)(CO)(PPh₃)L]NOₓ (where L = MeOH or MeCN and x = 2 or 3), were isolated and characterized by elemental analysis, IR, and NMR. The compounds were made by reactions of [Fe(C₅H₅)(CO)₂]₂, Fe(C₅H₅)(CO)₂I, [Ru(C₅H₅)(CO)₂]₂, and Fe(C₅H₅)(CO)(PPh₃)I with silver nitrite. The molecular and packing structures of Fe(C₅H₅)(CO)₂(NO₂) and Ru(C₅H₅)(CO)₂(NO₂) were determined by single-crystal X-ray diffractometry at -100°C and 26°C, respectively. Although stable at low temperature, Fe(C₅H₅)(CO)₂(NO₂) and Fe(C₅H₅)(CO)(PPh₃)(NO₂) decomposed at room temperature with evolution of CO₂ and concomitant formation of unstable metal nitrosyl complexes. In the case of Fe(C₅H₅)(CO)₂(NO₂), the mixture of products included Fe(C₅H₅)(CO)(NO), [Fe(C₅H₅)(NO)]₂, Fe(C₅H₅)₂, N₂O, CO, intractable material, and [Fe(C₅H₅)(CO)₂]₂. The kinetics of the oxygen transfer reactions of Fe(C₅H₅)(CO)₂(NO₂) and Fe(C₅H₅)(CO)(PPh₃)(NO₂) have been studied by NMR and IR of the solution, by IR and manometry of the gas phase, and by IR and elemental analysis of the intractable residues. The enthalpies and entropies of activation were obtained from Eyring plots of the reaction rate constants of Fe(C₅H₅)(CO)₂(NO₂) at 20, 30, and 40°C. Ru(C₅H₅)(CO)₂(NO₂) decomposes slowly with evolution of CO₂ at 40°C. In addition to the experiments outlined above, the dissertation includes discussions of the coordination chemistry of the new compounds in light of the few reports of other nitro organometallics and the calculations of molecular orbitals and energies. Also, the angular orientation of the basicity of the nitrite ion was probed by extended Huckel calculations of the orbital energies of hydrogen nitrite as the proton was moved around the nitrite ion. Lastly, ⁵⁷Fe-¹³P spin-spin coupling was measured in Fe(CO)₄(PPh₃) by ³¹P NMR.
Type:
text; Dissertation-Reproduction (electronic)
Degree Name:
Ph.D.
Degree Level:
doctoral
Degree Program:
Chemistry; Graduate College
Degree Grantor:
University of Arizona
Advisor:
Feltham, Robert D.

Full metadata record

DC FieldValue Language
dc.language.isoenen_US
dc.titleCarbonyl cyclopentadienylnitro complexes of iron and ruthenium and their oxygen atom transfer reactions.en_US
dc.creatorHansen, Craig Allen.en_US
dc.contributor.authorHansen, Craig Allen.en_US
dc.date.issued1988en_US
dc.publisherThe University of Arizona.en_US
dc.rightsCopyright © is held by the author. Digital access to this material is made possible by the University Libraries, University of Arizona. Further transmission, reproduction or presentation (such as public display or performance) of protected items is prohibited except with permission of the author.en_US
dc.description.abstractNew and reactive nitro organometallics, Fe(C₅H₅)(CO)₂(NO₂), Ru(C₅H₅)(CO)₂(NO₂), their nitrogen-15 derivatives, Fe(C₅H₅)(CO)(PPh₃)(NO₂), and [Fe(C₅H₅)(CO)(PPh₃)L]NOₓ (where L = MeOH or MeCN and x = 2 or 3), were isolated and characterized by elemental analysis, IR, and NMR. The compounds were made by reactions of [Fe(C₅H₅)(CO)₂]₂, Fe(C₅H₅)(CO)₂I, [Ru(C₅H₅)(CO)₂]₂, and Fe(C₅H₅)(CO)(PPh₃)I with silver nitrite. The molecular and packing structures of Fe(C₅H₅)(CO)₂(NO₂) and Ru(C₅H₅)(CO)₂(NO₂) were determined by single-crystal X-ray diffractometry at -100°C and 26°C, respectively. Although stable at low temperature, Fe(C₅H₅)(CO)₂(NO₂) and Fe(C₅H₅)(CO)(PPh₃)(NO₂) decomposed at room temperature with evolution of CO₂ and concomitant formation of unstable metal nitrosyl complexes. In the case of Fe(C₅H₅)(CO)₂(NO₂), the mixture of products included Fe(C₅H₅)(CO)(NO), [Fe(C₅H₅)(NO)]₂, Fe(C₅H₅)₂, N₂O, CO, intractable material, and [Fe(C₅H₅)(CO)₂]₂. The kinetics of the oxygen transfer reactions of Fe(C₅H₅)(CO)₂(NO₂) and Fe(C₅H₅)(CO)(PPh₃)(NO₂) have been studied by NMR and IR of the solution, by IR and manometry of the gas phase, and by IR and elemental analysis of the intractable residues. The enthalpies and entropies of activation were obtained from Eyring plots of the reaction rate constants of Fe(C₅H₅)(CO)₂(NO₂) at 20, 30, and 40°C. Ru(C₅H₅)(CO)₂(NO₂) decomposes slowly with evolution of CO₂ at 40°C. In addition to the experiments outlined above, the dissertation includes discussions of the coordination chemistry of the new compounds in light of the few reports of other nitro organometallics and the calculations of molecular orbitals and energies. Also, the angular orientation of the basicity of the nitrite ion was probed by extended Huckel calculations of the orbital energies of hydrogen nitrite as the proton was moved around the nitrite ion. Lastly, ⁵⁷Fe-¹³P spin-spin coupling was measured in Fe(CO)₄(PPh₃) by ³¹P NMR.en_US
dc.typetexten_US
dc.typeDissertation-Reproduction (electronic)en_US
thesis.degree.namePh.D.en_US
thesis.degree.leveldoctoralen_US
thesis.degree.disciplineChemistryen_US
thesis.degree.disciplineGraduate Collegeen_US
thesis.degree.grantorUniversity of Arizonaen_US
dc.contributor.advisorFeltham, Robert D.en_US
dc.contributor.committeememberEnemark, John H.en_US
dc.contributor.committeememberRund, John V.en_US
dc.contributor.committeememberSalzman, W. R.en_US
dc.contributor.committeememberBernath, Peter F.en_US
dc.identifier.proquest8824274en_US
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