{"id":{"repo_id":"wustl","oai_identifier":"oai:openscholarship.wustl.edu:art_sci_etds-1469"},"canonical_url":"https://search.dev.ndltd.org/etd/wustl/oai:openscholarship.wustl.edu:art_sci_etds-1469","repository":{"repo_id":"wustl","name":"Washington University in St. Louis","base_url":"https://openscholarship.wustl.edu/do/oai/"},"display":{"title":"Synthesis, Structure, Spectroscopy, and Reactivity of Azapentadienyl-Ruthenium-Phosphine Complexes","abstract":"This dissertation focuses on the systematic synthesis of ¬bis-azapentadienyl-ruthenium-phosphine complexes. The synthetic approach involves the treatment of Cl2Ru(PPh3)3 with potassium tert-butylazapentadienide reagent. The reactivity of this parent compound with other 2e- donor ligands is investigated. These resultant complexes' reactivity with triflic acid is also studied.Treatment of Cl2Ru(PPh3)3 with potassium tert-butylazapentadienide produces [(1,2,3-η3)-5-tert-butylazapentadienyl]2Ru(PPh3)2 (1). Compound 1 undergoes single substitution of one of the triphenylphosphines when treated with PMe3, dmpe, P(OMe)3, CNCMe3, CO, and PEt3 at room temperature, resulting in [(1,2,3-η3)-5-tert-butylazapentadienyl]2Ru(PPh3)(L) (2, L = PMe3; 3, L= dmpe; 4, L = P(OMe)3; 5, L = CNCMe3; 6, L = CO; 7, L = PEt3). By increasing the reaction time of 1 with PEt3, double substitution of both triphenylphosphines occurs, resulting in [(1,2,3-η3)-5-tert-butylazapentadienyl]2Ru(PEt3)2 (8). Compounds 1 - 8 possess a pseudo-octahedral geometry where both ancillary ligands sit trans to the C3's of the azapentadienyl ligands. Compounds 1 - 4, 7 and 8 exhibit a ligand orientation in which both ancillary ligands sit in the mouth of each azapentadienyl ligand, denoted as mC3/mC3. In contrast, 5 exhibits a ligand arrangement where the PPh3 sits in the mouth of one azapentadienyl ligand while CNCMe3 sits on the backbone of the other azapentadienyl ligand.Other double substitution reactions occur when 1 is treated with PMe3, P(OMe)3, and dmpe in THF at reflux, resulting in [(1,2,3-η3)-5-tert-butylazapentadienyl]2Ru(L)x (9, L = PMe3, x = 2; 10, L = P(OMe3), x = 2; 11, L = dmpe, x = 1). Compounds 9 and 10 exist in solution as an equilibrium mixture of two structural isomers. The two isomers in solution have either a mC3/mC3 or mC3/bC1 ligand orientation.Treatment of 8, 9 and 10 with triflic acid results in dicationic products, {[(1,2,3-η3)-(CH2CHCHCH=N(H)(CMe3)]2Ru(L)2}2+(-O3SCF3)2 (12, L = PEt3; 13, L = PMe3; 14, L = P(OMe)3), in which both azapentadienyl nitrogen atoms have been protonated. The protonated product, 12, shows a ligand conversion from mC3/mC3 (seen in 8) to mC3/bC3. Upon protonation, 9 and 10 each convert to a single isomer, 12 and 13, respectively. Like 12, compound 13 possesses a mC3/bC3 orientation while 14 has a ligand orientation in which the azapentadienyl ligands appear to be mC3/mC3. Treatment of 2, 4 and 5 with triflic acid results in multiple isomers of the diprotonated {[(1,2,3-η3)-CH2CHCHCH=N(H)(CMe3)]2Ru(PPh3)(L)}2+(-O3SCF3)2 (15, L = PMe3; 16, L = P(OMe)3; 17, L = CNCMe3). All of the compounds have been characterized, in part, by NMR spectroscopy, and the structures of 2, 4, 5, 7, 8, and 12 have been confirmed by single-crystal X-ray diffraction.","abstract_html":"This dissertation focuses on the systematic synthesis of ¬bis-azapentadienyl-ruthenium-phosphine complexes. The synthetic approach involves the treatment of Cl2Ru(PPh3)3 with potassium tert-butylazapentadienide reagent. The reactivity of this parent compound with other 2e- donor ligands is investigated. These resultant complexes' reactivity with triflic acid is also studied.Treatment of Cl2Ru(PPh3)3 with potassium tert-butylazapentadienide produces [(1,2,3-η3)-5-tert-butylazapentadienyl]2Ru(PPh3)2 (1). Compound 1 undergoes single substitution of one of the triphenylphosphines when treated with PMe3, dmpe, P(OMe)3, CNCMe3, CO, and PEt3 at room temperature, resulting in [(1,2,3-η3)-5-tert-butylazapentadienyl]2Ru(PPh3)(L) (2, L = PMe3; 3, L= dmpe; 4, L = P(OMe)3; 5, L = CNCMe3; 6, L = CO; 7, L = PEt3). By increasing the reaction time of 1 with PEt3, double substitution of both triphenylphosphines occurs, resulting in [(1,2,3-η3)-5-tert-butylazapentadienyl]2Ru(PEt3)2 (8). Compounds 1 - 8 possess a pseudo-octahedral geometry where both ancillary ligands sit trans to the C3's of the azapentadienyl ligands. Compounds 1 - 4, 7 and 8 exhibit a ligand orientation in which both ancillary ligands sit in the mouth of each azapentadienyl ligand, denoted as mC3/mC3. In contrast, 5 exhibits a ligand arrangement where the PPh3 sits in the mouth of one azapentadienyl ligand while CNCMe3 sits on the backbone of the other azapentadienyl ligand.Other double substitution reactions occur when 1 is treated with PMe3, P(OMe)3, and dmpe in THF at reflux, resulting in [(1,2,3-η3)-5-tert-butylazapentadienyl]2Ru(L)x (9, L = PMe3, x = 2; 10, L = P(OMe3), x = 2; 11, L = dmpe, x = 1). Compounds 9 and 10 exist in solution as an equilibrium mixture of two structural isomers. The two isomers in solution have either a mC3/mC3 or mC3/bC1 ligand orientation.Treatment of 8, 9 and 10 with triflic acid results in dicationic products, {[(1,2,3-η3)-(CH2CHCHCH=N(H)(CMe3)]2Ru(L)2}2+(-O3SCF3)2 (12, L = PEt3; 13, L = PMe3; 14, L = P(OMe)3), in which both azapentadienyl nitrogen atoms have been protonated. The protonated product, 12, shows a ligand conversion from mC3/mC3 (seen in 8) to mC3/bC3. Upon protonation, 9 and 10 each convert to a single isomer, 12 and 13, respectively. Like 12, compound 13 possesses a mC3/bC3 orientation while 14 has a ligand orientation in which the azapentadienyl ligands appear to be mC3/mC3. Treatment of 2, 4 and 5 with triflic acid results in multiple isomers of the diprotonated {[(1,2,3-η3)-CH2CHCHCH=N(H)(CMe3)]2Ru(PPh3)(L)}2+(-O3SCF3)2 (15, L = PMe3; 16, L = P(OMe)3; 17, L = CNCMe3). All of the compounds have been characterized, in part, by NMR spectroscopy, and the structures of 2, 4, 5, 7, 8, and 12 have been confirmed by single-crystal X-ray diffraction.","abstract_has_math":false,"creators":["Stouffer, Meghan Leigh"],"institution":null,"degree_name":"Doctor of Philosophy (PhD)","degree_level":"Dissertation","degree_discipline":"Chemistry","degree_department":null,"school":null,"contributors":["John R Bleeke","Bill Buhro, Liviu Mirica, Sophia Hayes, Nigam Rath"],"advisors":[],"committee_chairs":[],"committee_members":[],"year":2015,"date_issued":"2015-05-15T07:00:00Z","date_published":"2015-05-15T07:00:00Z","updated_at":"2026-07-24T06:12:08Z","subjects":["Organometallics","Chemistry"],"languages":["English (en)"],"rights":["I have not registered my thesis with the U.S. Copyright Office, and do not intend to."],"rights_urls":[],"identifier_entries":[{"key":"dc:identifier","label":"Identifier","values":["https://openscholarship.wustl.edu/art_sci_etds/469"],"render_values":[{"text":"https://openscholarship.wustl.edu/art_sci_etds/469","href":"https://openscholarship.wustl.edu/art_sci_etds/469","code":true}]}]},"links":{"outbound_url":"https://doi.org/10.7936/K79S1P7R","outbound_label":"DOI","outbound_source":"dc:identifier"},"metadata_groups":[{"id":"people","label":"People","entries":[{"key":"dc:contributor","label":"Contributor","values":["John R Bleeke","Bill Buhro, Liviu Mirica, Sophia Hayes, Nigam Rath"]},{"key":"dc:creator","label":"Author","values":["Stouffer, Meghan Leigh"]}]},{"id":"academic_context","label":"Academic Context","entries":[{"key":"dc:date.available","label":"Dc Date Available","values":["2015-06-19T07:00:00Z"]},{"key":"thesis:degree_discipline","label":"Discipline","values":["Chemistry","Graduate School of Arts and Sciences"]},{"key":"thesis:degree_level","label":"Degree Level","values":["Dissertation"]},{"key":"thesis:degree_name","label":"Degree Name","values":["Doctor of Philosophy (PhD)"]}]},{"id":"subjects_keywords","label":"Subjects and Keywords","entries":[{"key":"dc:subject","label":"Dc Subject","values":["Organometallics","Chemistry"]}]},{"id":"language_rights","label":"Language and Rights","entries":[{"key":"dc:language","label":"Dc Language","values":["English (en)"]},{"key":"dc:rights","label":"Dc Rights","values":["I have not registered my thesis with the U.S. Copyright Office, and do not intend to."]}]},{"id":"identifiers","label":"Identifiers","entries":[{"key":"dc:identifier","label":"Identifier","values":["https://doi.org/10.7936/K79S1P7R","https://openscholarship.wustl.edu/art_sci_etds/469"]}]},{"id":"additional","label":"Additional Metadata","entries":[{"key":"dc:description","label":"Description","values":["Permanent URL: https://doi.org/10.7936/K79S1P7R"]},{"key":"dc:description.abstract","label":"Abstract","values":["This dissertation focuses on the systematic synthesis of ¬bis-azapentadienyl-ruthenium-phosphine complexes. The synthetic approach involves the treatment of Cl2Ru(PPh3)3 with potassium tert-butylazapentadienide reagent. The reactivity of this parent compound with other 2e- donor ligands is investigated. These resultant complexes' reactivity with triflic acid is also studied.Treatment of Cl2Ru(PPh3)3 with potassium tert-butylazapentadienide produces [(1,2,3-η3)-5-tert-butylazapentadienyl]2Ru(PPh3)2 (1). Compound 1 undergoes single substitution of one of the triphenylphosphines when treated with PMe3, dmpe, P(OMe)3, CNCMe3, CO, and PEt3 at room temperature, resulting in [(1,2,3-η3)-5-tert-butylazapentadienyl]2Ru(PPh3)(L) (2, L = PMe3; 3, L= dmpe; 4, L = P(OMe)3; 5, L = CNCMe3; 6, L = CO; 7, L = PEt3). By increasing the reaction time of 1 with PEt3, double substitution of both triphenylphosphines occurs, resulting in [(1,2,3-η3)-5-tert-butylazapentadienyl]2Ru(PEt3)2 (8). Compounds 1 - 8 possess a pseudo-octahedral geometry where both ancillary ligands sit trans to the C3's of the azapentadienyl ligands. Compounds 1 - 4, 7 and 8 exhibit a ligand orientation in which both ancillary ligands sit in the mouth of each azapentadienyl ligand, denoted as mC3/mC3. In contrast, 5 exhibits a ligand arrangement where the PPh3 sits in the mouth of one azapentadienyl ligand while CNCMe3 sits on the backbone of the other azapentadienyl ligand.Other double substitution reactions occur when 1 is treated with PMe3, P(OMe)3, and dmpe in THF at reflux, resulting in [(1,2,3-η3)-5-tert-butylazapentadienyl]2Ru(L)x (9, L = PMe3, x = 2; 10, L = P(OMe3), x = 2; 11, L = dmpe, x = 1). Compounds 9 and 10 exist in solution as an equilibrium mixture of two structural isomers. The two isomers in solution have either a mC3/mC3 or mC3/bC1 ligand orientation.Treatment of 8, 9 and 10 with triflic acid results in dicationic products, {[(1,2,3-η3)-(CH2CHCHCH=N(H)(CMe3)]2Ru(L)2}2+(-O3SCF3)2 (12, L = PEt3; 13, L = PMe3; 14, L = P(OMe)3), in which both azapentadienyl nitrogen atoms have been protonated. The protonated product, 12, shows a ligand conversion from mC3/mC3 (seen in 8) to mC3/bC3. Upon protonation, 9 and 10 each convert to a single isomer, 12 and 13, respectively. Like 12, compound 13 possesses a mC3/bC3 orientation while 14 has a ligand orientation in which the azapentadienyl ligands appear to be mC3/mC3. Treatment of 2, 4 and 5 with triflic acid results in multiple isomers of the diprotonated {[(1,2,3-η3)-CH2CHCHCH=N(H)(CMe3)]2Ru(PPh3)(L)}2+(-O3SCF3)2 (15, L = PMe3; 16, L = P(OMe)3; 17, L = CNCMe3). All of the compounds have been characterized, in part, by NMR spectroscopy, and the structures of 2, 4, 5, 7, 8, and 12 have been confirmed by single-crystal X-ray diffraction."]},{"key":"dc:title","label":"Title","values":["Synthesis, Structure, Spectroscopy, and Reactivity of Azapentadienyl-Ruthenium-Phosphine Complexes"]}]}],"canonical_facts":{"dc:contributor":["John R Bleeke","Bill Buhro, Liviu Mirica, Sophia Hayes, Nigam Rath"],"dc:creator":["Stouffer, Meghan Leigh"],"dc:date.available":["2015-06-19T07:00:00Z"],"dc:description":["Permanent URL: https://doi.org/10.7936/K79S1P7R"],"dc:description.abstract":["This dissertation focuses on the systematic synthesis of ¬bis-azapentadienyl-ruthenium-phosphine complexes. The synthetic approach involves the treatment of Cl2Ru(PPh3)3 with potassium tert-butylazapentadienide reagent. The reactivity of this parent compound with other 2e- donor ligands is investigated. These resultant complexes' reactivity with triflic acid is also studied.Treatment of Cl2Ru(PPh3)3 with potassium tert-butylazapentadienide produces [(1,2,3-η3)-5-tert-butylazapentadienyl]2Ru(PPh3)2 (1). Compound 1 undergoes single substitution of one of the triphenylphosphines when treated with PMe3, dmpe, P(OMe)3, CNCMe3, CO, and PEt3 at room temperature, resulting in [(1,2,3-η3)-5-tert-butylazapentadienyl]2Ru(PPh3)(L) (2, L = PMe3; 3, L= dmpe; 4, L = P(OMe)3; 5, L = CNCMe3; 6, L = CO; 7, L = PEt3). By increasing the reaction time of 1 with PEt3, double substitution of both triphenylphosphines occurs, resulting in [(1,2,3-η3)-5-tert-butylazapentadienyl]2Ru(PEt3)2 (8). Compounds 1 - 8 possess a pseudo-octahedral geometry where both ancillary ligands sit trans to the C3's of the azapentadienyl ligands. Compounds 1 - 4, 7 and 8 exhibit a ligand orientation in which both ancillary ligands sit in the mouth of each azapentadienyl ligand, denoted as mC3/mC3. In contrast, 5 exhibits a ligand arrangement where the PPh3 sits in the mouth of one azapentadienyl ligand while CNCMe3 sits on the backbone of the other azapentadienyl ligand.Other double substitution reactions occur when 1 is treated with PMe3, P(OMe)3, and dmpe in THF at reflux, resulting in [(1,2,3-η3)-5-tert-butylazapentadienyl]2Ru(L)x (9, L = PMe3, x = 2; 10, L = P(OMe3), x = 2; 11, L = dmpe, x = 1). Compounds 9 and 10 exist in solution as an equilibrium mixture of two structural isomers. The two isomers in solution have either a mC3/mC3 or mC3/bC1 ligand orientation.Treatment of 8, 9 and 10 with triflic acid results in dicationic products, {[(1,2,3-η3)-(CH2CHCHCH=N(H)(CMe3)]2Ru(L)2}2+(-O3SCF3)2 (12, L = PEt3; 13, L = PMe3; 14, L = P(OMe)3), in which both azapentadienyl nitrogen atoms have been protonated. The protonated product, 12, shows a ligand conversion from mC3/mC3 (seen in 8) to mC3/bC3. Upon protonation, 9 and 10 each convert to a single isomer, 12 and 13, respectively. Like 12, compound 13 possesses a mC3/bC3 orientation while 14 has a ligand orientation in which the azapentadienyl ligands appear to be mC3/mC3. Treatment of 2, 4 and 5 with triflic acid results in multiple isomers of the diprotonated {[(1,2,3-η3)-CH2CHCHCH=N(H)(CMe3)]2Ru(PPh3)(L)}2+(-O3SCF3)2 (15, L = PMe3; 16, L = P(OMe)3; 17, L = CNCMe3). All of the compounds have been characterized, in part, by NMR spectroscopy, and the structures of 2, 4, 5, 7, 8, and 12 have been confirmed by single-crystal X-ray diffraction."],"dc:identifier":["https://doi.org/10.7936/K79S1P7R","https://openscholarship.wustl.edu/art_sci_etds/469"],"dc:language":["English (en)"],"dc:rights":["I have not registered my thesis with the U.S. Copyright Office, and do not intend to."],"dc:subject":["Organometallics","Chemistry"],"dc:title":["Synthesis, Structure, Spectroscopy, and Reactivity of Azapentadienyl-Ruthenium-Phosphine Complexes"],"thesis:degree_discipline":["Chemistry","Graduate School of Arts and Sciences"],"thesis:degree_level":["Dissertation"],"thesis:degree_name":["Doctor of Philosophy (PhD)"]},"updated_at":"2026-07-24T06:12:08Z"}