Persistent Link:
http://hdl.handle.net/10150/184733
Title:
Molybdenum, tungsten and rhodium complexes of nitrogen-oxides.
Author:
Rajaseelan, Rajaratnam Edward.
Issue Date:
1989
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:
Complexes of the type MX(η²-NO₃)(CO)₂(PPh₃)₂, (M = Mo, X = Cl, Br; M = W, X = Br) were prepared from the reactions of MX₂(CO)₂(PPh₃)₂ with ammonium nitrate in acetone. The complexes were characterized by elemental analyses, ¹⁵N labelling, infrared and NMR spectroscopy. The nitrate ligand is bidentate and the complexes are seven-coordinate. Novel nitrite complexes of molybdenum and tungsten of the type M(NO₂)₂(PPh₃)₂ were prepared. The compounds were characterized by elemental analyses, ¹⁵N labelling, infrared and multinuclear NMR spectroscopy. Both NO₂ ligands are chelating and the two NO₂, PPh₃ and CO ligands are equivalent. Molybdenum dinitrosyl complexes were synthesized by the reduction of nitrate ions. The crystal structure of cis-dinitrosyl-cis-dichloro-trans-bis-(triphenylphosphine)molybdenum(II) was determined by x-ray diffraction. Both the nitrosyl groups are linear. Mo(NO)₂Cl₂(OPPh₃)₂ and Mo(NO)₂Cl(NO₃)(OPPh₃)₂ were synthesized by the reaction of MoCl(η²-NO₃)(CO)₂(PPh₃)₂ with NO in acetone/toluene mixture. The nitrosyl ligands are linear and the phosphineoxide ligands are cis to each other. The dinitrite complex Rh(NO)(NO₂)₂(PPh₃)₂ of the series Rh(NO)X₂(PPh₃)₂ (X - monodentate anions) was prepared as a direct derivative of Rh(NO)Cl₂(PPh₃)₂ by its reaction with sodium nitrite. The complex is square pyramidal with an apical nitrosyl ligand. The two NO₂ groups are present as the nitro and the nitrito group. Rh(NO)(NO₂)₂(PPh₃) reacted with oxygen and formed Rh(NO₃)₃(PPh₃)₂. The reaction of Rh(NO)(NO₂)₂(PPh₃)₂ with CO in acetonitrile produced Rh(CO)(NO₂)(PPh₃)₂. The complex Rh(CO)(NO₂)(PPh₃)₂ is square planar with the phosphine ligands in the trans positions.
Type:
text; Dissertation-Reproduction (electronic)
Keywords:
Transition metal complexes.; Nitrogen oxides.
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.titleMolybdenum, tungsten and rhodium complexes of nitrogen-oxides.en_US
dc.creatorRajaseelan, Rajaratnam Edward.en_US
dc.contributor.authorRajaseelan, Rajaratnam Edward.en_US
dc.date.issued1989en_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.abstractComplexes of the type MX(η²-NO₃)(CO)₂(PPh₃)₂, (M = Mo, X = Cl, Br; M = W, X = Br) were prepared from the reactions of MX₂(CO)₂(PPh₃)₂ with ammonium nitrate in acetone. The complexes were characterized by elemental analyses, ¹⁵N labelling, infrared and NMR spectroscopy. The nitrate ligand is bidentate and the complexes are seven-coordinate. Novel nitrite complexes of molybdenum and tungsten of the type M(NO₂)₂(PPh₃)₂ were prepared. The compounds were characterized by elemental analyses, ¹⁵N labelling, infrared and multinuclear NMR spectroscopy. Both NO₂ ligands are chelating and the two NO₂, PPh₃ and CO ligands are equivalent. Molybdenum dinitrosyl complexes were synthesized by the reduction of nitrate ions. The crystal structure of cis-dinitrosyl-cis-dichloro-trans-bis-(triphenylphosphine)molybdenum(II) was determined by x-ray diffraction. Both the nitrosyl groups are linear. Mo(NO)₂Cl₂(OPPh₃)₂ and Mo(NO)₂Cl(NO₃)(OPPh₃)₂ were synthesized by the reaction of MoCl(η²-NO₃)(CO)₂(PPh₃)₂ with NO in acetone/toluene mixture. The nitrosyl ligands are linear and the phosphineoxide ligands are cis to each other. The dinitrite complex Rh(NO)(NO₂)₂(PPh₃)₂ of the series Rh(NO)X₂(PPh₃)₂ (X - monodentate anions) was prepared as a direct derivative of Rh(NO)Cl₂(PPh₃)₂ by its reaction with sodium nitrite. The complex is square pyramidal with an apical nitrosyl ligand. The two NO₂ groups are present as the nitro and the nitrito group. Rh(NO)(NO₂)₂(PPh₃) reacted with oxygen and formed Rh(NO₃)₃(PPh₃)₂. The reaction of Rh(NO)(NO₂)₂(PPh₃)₂ with CO in acetonitrile produced Rh(CO)(NO₂)(PPh₃)₂. The complex Rh(CO)(NO₂)(PPh₃)₂ is square planar with the phosphine ligands in the trans positions.en_US
dc.typetexten_US
dc.typeDissertation-Reproduction (electronic)en_US
dc.subjectTransition metal complexes.en_US
dc.subjectNitrogen oxides.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.committeememberBates, Roberten_US
dc.contributor.committeememberMash, Eugeneen_US
dc.contributor.committeememberRund, Johnen_US
dc.identifier.proquest8919055en_US
dc.identifier.oclc702461786en_US
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