{"id":{"repo_id":"salford","oai_identifier":"oai:salford-repository.worktribe.com:1337252"},"canonical_url":"https://search.dev.ndltd.org/etd/salford/oai:salford-repository.worktribe.com:1337252","repository":{"repo_id":"salford","name":"U. of Salford","base_url":"https://salford-repository.worktribe.com/oaiprovider"},"display":{"title":"Utilisation of halophosphine and aminophosphine ligands in organoruthenium chemistry","abstract":"This thesis concerns the syntheses and reactivity of areneruthenium complexescontaining halophosphine and aminophosphine ligands. Methylcyclopentadienylrutheniumchemistry is also developed together with corresponding tertbutylcyclopentadienylrutheniumchemistry. All the new compounds prepared arepseudo-octahedral with the arene or cyclopentadienyl ligand being facially coordinated.The first chapter contains a literature review of the chemistry of the rutheniumcomplex [RuCl 2(r| 6 -/?-cymene)] 2 , which is one of our starting materials. The chemistryof the ligands tris(dimethylamino)phosphine, trifluorophosphine, trichlorophosphine,tribromophosphine, dimethylaminodifluorophosphine and tert-butyldichlorophosphineis also detailed.The second chapter reports the syntheses and reactivity of the neutral compounds[RuX 2 (r| 6-/>cymene)P(NMe 2 ) 3 ] (X= Cl, Br, and I) and the cationic tris-(dimethylamino)phosphine complexes [RuCl(r| 6 -/?-cymene)P(NMe2 ) 3 (L)] (L = CO,CN'Bu, PPh3 , P(OPh3 ) 3 , P(OCH 3 ) 3 SMe 2 ). The new complexes were characterized bymultinuclear N.M.R spectroscopy; x-ray crystallographic structure determinations werecarried out on [RuCl2 (r) 6-/?-cymene)P(NMe 2 ) 3 ], [RuI 2 (r| 6 -/>-cymene)P(NMe 2 ) 3 ],[RuCl(nVcymene)P(NMe2 ) 3 (CO)]PF 6 , [RuCl(Ti 6 -p-cymene)P(NMe 2 ) 3 S(CH 3 ) 2 ]PF 6 .and [RuCl 2 (n 6 -/7-cymene)(HNMe 2 )].The third chapter describes the syntheses and reactivity of [RuX 2 (r| 6 -pcymene)P(Z) 3 ] (X= Cl, Br, and I, Z = Cl, Br. and F). The generation oftrifluorophosphine gas on a small scale is described. The observation of halogen exchange between the ruthenium centre and halophosphines is reported and the trendsin 'j(P-F) are described in the two series [RuX 2 (n 6-/>cymene)(PF 3 )] and [RuX 2 (n 6 -/?-cymene)(PF 2 {NMe 2 })].The fourth chapter contains the syntheses of two series of newalkylcyclopentadienyl complexes [(r| 5 -tert-BuCp)Ru(PPh3 )(L)Cl] and [(ry-MeCp)Ru(PPh3 )(L)Cl], (L = CO, CN'Bu, PPh 3 ) and [[(r| 5 -ter/-BuCp)Ru((L') 2 Cl] (L 1 =P(OPh 3 ) 3 , P(OCH 3 ) 3 , PPh3 , and dppm). Some hydride and cationic complexes havebeen produced from these precursors. The chapter ends with a spectroscopiccomparison of alkylcyclopentadienylruthenium derivatives.The fifth chapter contains all the experimental work carried out for chapters two,three, and fourThe sixth chapter contains suggestions for future workThe appendices contain the x-ray crystallographic metric data for nine newcompounds: [RuCl 2 (n 6 -p-cymene)P(NMe 2 ) 3 J, [RuI 2 (n 6 -p-cymene)P(NMe2 ) 3 J, [RuCl(n 6 -/7-cymene)P(NMe 2 ) 3 (CO)]PF 6 , [RuCl(r| 6 -/7-cymene)P(NMe 2 )3 S(CH 3 ) 2 ]PF 6 , [RuCl 2 (n 6 -p-cymene)(HNMe 2 )], [RuCl 2 (r| 6 -p-cymene)PF 3 ], [RuCl 2 (n 6 -p-cymene)PF 2 (NMe 2 )],[(r| 5 -tert-BuCp)Ru(PPh 3 )2 (CN t Bu)]BF4 , and[[(Ti 5 -MeCp)Ru(dppf)P(OCH 3 ) 3 ]BF4 .","abstract_html":"This thesis concerns the syntheses and reactivity of areneruthenium complexescontaining halophosphine and aminophosphine ligands. Methylcyclopentadienylrutheniumchemistry is also developed together with corresponding tertbutylcyclopentadienylrutheniumchemistry. All the new compounds prepared arepseudo-octahedral with the arene or cyclopentadienyl ligand being facially coordinated.The first chapter contains a literature review of the chemistry of the rutheniumcomplex [RuCl 2(r| 6 -/?-cymene)] 2 , which is one of our starting materials. The chemistryof the ligands tris(dimethylamino)phosphine, trifluorophosphine, trichlorophosphine,tribromophosphine, dimethylaminodifluorophosphine and tert-butyldichlorophosphineis also detailed.The second chapter reports the syntheses and reactivity of the neutral compounds[RuX 2 (r| 6-/>cymene)P(NMe 2 ) 3 ] (X= Cl, Br, and I) and the cationic tris-(dimethylamino)phosphine complexes [RuCl(r| 6 -/?-cymene)P(NMe2 ) 3 (L)] (L = CO,CN'Bu, PPh3 , P(OPh3 ) 3 , P(OCH 3 ) 3 SMe 2 ). The new complexes were characterized bymultinuclear N.M.R spectroscopy; x-ray crystallographic structure determinations werecarried out on [RuCl2 (r) 6-/?-cymene)P(NMe 2 ) 3 ], [RuI 2 (r| 6 -/>-cymene)P(NMe 2 ) 3 ],[RuCl(nVcymene)P(NMe2 ) 3 (CO)]PF 6 , [RuCl(Ti 6 -p-cymene)P(NMe 2 ) 3 S(CH 3 ) 2 ]PF 6 .and [RuCl 2 (n 6 -/7-cymene)(HNMe 2 )].The third chapter describes the syntheses and reactivity of [RuX 2 (r| 6 -pcymene)P(Z) 3 ] (X= Cl, Br, and I, Z = Cl, Br. and F). The generation oftrifluorophosphine gas on a small scale is described. The observation of halogen exchange between the ruthenium centre and halophosphines is reported and the trendsin 'j(P-F) are described in the two series [RuX 2 (n 6-/>cymene)(PF 3 )] and [RuX 2 (n 6 -/?-cymene)(PF 2 {NMe 2 })].The fourth chapter contains the syntheses of two series of newalkylcyclopentadienyl complexes [(r| 5 -tert-BuCp)Ru(PPh3 )(L)Cl] and [(ry-MeCp)Ru(PPh3 )(L)Cl], (L = CO, CN'Bu, PPh 3 ) and [[(r| 5 -ter/-BuCp)Ru((L') 2 Cl] (L 1 =P(OPh 3 ) 3 , P(OCH 3 ) 3 , PPh3 , and dppm). Some hydride and cationic complexes havebeen produced from these precursors. The chapter ends with a spectroscopiccomparison of alkylcyclopentadienylruthenium derivatives.The fifth chapter contains all the experimental work carried out for chapters two,three, and fourThe sixth chapter contains suggestions for future workThe appendices contain the x-ray crystallographic metric data for nine newcompounds: [RuCl 2 (n 6 -p-cymene)P(NMe 2 ) 3 J, [RuI 2 (n 6 -p-cymene)P(NMe2 ) 3 J, [RuCl(n 6 -/7-cymene)P(NMe 2 ) 3 (CO)]PF 6 , [RuCl(r| 6 -/7-cymene)P(NMe 2 )3 S(CH 3 ) 2 ]PF 6 , [RuCl 2 (n 6 -p-cymene)(HNMe 2 )], [RuCl 2 (r| 6 -p-cymene)PF 3 ], [RuCl 2 (n 6 -p-cymene)PF 2 (NMe 2 )],[(r| 5 -tert-BuCp)Ru(PPh 3 )2 (CN t Bu)]BF4 , and[[(Ti 5 -MeCp)Ru(dppf)P(OCH 3 ) 3 ]BF4 .","abstract_has_math":false,"creators":["Boshaala, AMA"],"institution":null,"degree_name":null,"degree_level":"Doctoral (Level 8)","degree_discipline":null,"degree_department":null,"school":null,"contributors":[],"advisors":[],"committee_chairs":[],"committee_members":[],"year":2008,"date_issued":"2008","date_published":"2008","updated_at":"2026-07-24T04:26:09Z","subjects":[],"languages":["en"],"rights":[],"rights_urls":[],"identifier_entries":[{"key":"dc:identifier","label":"Identifier","values":["oai:salford-repository.worktribe.com:1337252"],"render_values":[{"text":"oai:salford-repository.worktribe.com:1337252","href":null,"code":true}]}]},"links":{"outbound_url":null,"outbound_label":null,"outbound_source":null},"metadata_groups":[{"id":"people","label":"People","entries":[{"key":"dc:contributor.sponsor","label":"Sponsor","values":["University of Salford"]},{"key":"dc:creator","label":"Author","values":["Boshaala, AMA"]}]},{"id":"academic_context","label":"Academic Context","entries":[{"key":"dc:date","label":"Dc Date","values":["2008-03-01"]},{"key":"dc:date.issued","label":"Date","values":["2008"]},{"key":"dc:relation.isreferencedby","label":"Dc Relation Isreferencedby","values":["https://salford-repository.worktribe.com/output/1337252"]},{"key":"dc:type","label":"Dc Type","values":["Thesis"]},{"key":"dc:type.qualificationlevel","label":"Dc Type Qualificationlevel","values":["Doctoral (Level 8)"]}]},{"id":"language_rights","label":"Language and Rights","entries":[{"key":"dc:language","label":"Dc Language","values":["en"]}]},{"id":"identifiers","label":"Identifiers","entries":[{"key":"dc:identifier","label":"Identifier","values":["oai:salford-repository.worktribe.com:1337252"]},{"key":"dc:identifier.uri","label":"Identifier URI","values":["https://salford-repository.worktribe.com/file/1337252/1/1090980X.pdf"]}]},{"id":"additional","label":"Additional Metadata","entries":[{"key":"dc:description.abstract","label":"Abstract","values":["This thesis concerns the syntheses and reactivity of areneruthenium complexescontaining halophosphine and aminophosphine ligands. Methylcyclopentadienylrutheniumchemistry is also developed together with corresponding tertbutylcyclopentadienylrutheniumchemistry. All the new compounds prepared arepseudo-octahedral with the arene or cyclopentadienyl ligand being facially coordinated.The first chapter contains a literature review of the chemistry of the rutheniumcomplex [RuCl 2(r| 6 -/?-cymene)] 2 , which is one of our starting materials. The chemistryof the ligands tris(dimethylamino)phosphine, trifluorophosphine, trichlorophosphine,tribromophosphine, dimethylaminodifluorophosphine and tert-butyldichlorophosphineis also detailed.The second chapter reports the syntheses and reactivity of the neutral compounds[RuX 2 (r| 6-/>cymene)P(NMe 2 ) 3 ] (X= Cl, Br, and I) and the cationic tris-(dimethylamino)phosphine complexes [RuCl(r| 6 -/?-cymene)P(NMe2 ) 3 (L)] (L = CO,CN'Bu, PPh3 , P(OPh3 ) 3 , P(OCH 3 ) 3 SMe 2 ). The new complexes were characterized bymultinuclear N.M.R spectroscopy; x-ray crystallographic structure determinations werecarried out on [RuCl2 (r) 6-/?-cymene)P(NMe 2 ) 3 ], [RuI 2 (r| 6 -/>-cymene)P(NMe 2 ) 3 ],[RuCl(nVcymene)P(NMe2 ) 3 (CO)]PF 6 , [RuCl(Ti 6 -p-cymene)P(NMe 2 ) 3 S(CH 3 ) 2 ]PF 6 .and [RuCl 2 (n 6 -/7-cymene)(HNMe 2 )].The third chapter describes the syntheses and reactivity of [RuX 2 (r| 6 -pcymene)P(Z) 3 ] (X= Cl, Br, and I, Z = Cl, Br. and F). The generation oftrifluorophosphine gas on a small scale is described. The observation of halogen exchange between the ruthenium centre and halophosphines is reported and the trendsin 'j(P-F) are described in the two series [RuX 2 (n 6-/>cymene)(PF 3 )] and [RuX 2 (n 6 -/?-cymene)(PF 2 {NMe 2 })].The fourth chapter contains the syntheses of two series of newalkylcyclopentadienyl complexes [(r| 5 -tert-BuCp)Ru(PPh3 )(L)Cl] and [(ry-MeCp)Ru(PPh3 )(L)Cl], (L = CO, CN'Bu, PPh 3 ) and [[(r| 5 -ter/-BuCp)Ru((L') 2 Cl] (L 1 =P(OPh 3 ) 3 , P(OCH 3 ) 3 , PPh3 , and dppm). Some hydride and cationic complexes havebeen produced from these precursors. The chapter ends with a spectroscopiccomparison of alkylcyclopentadienylruthenium derivatives.The fifth chapter contains all the experimental work carried out for chapters two,three, and fourThe sixth chapter contains suggestions for future workThe appendices contain the x-ray crystallographic metric data for nine newcompounds: [RuCl 2 (n 6 -p-cymene)P(NMe 2 ) 3 J, [RuI 2 (n 6 -p-cymene)P(NMe2 ) 3 J, [RuCl(n 6 -/7-cymene)P(NMe 2 ) 3 (CO)]PF 6 , [RuCl(r| 6 -/7-cymene)P(NMe 2 )3 S(CH 3 ) 2 ]PF 6 , [RuCl 2 (n 6 -p-cymene)(HNMe 2 )], [RuCl 2 (r| 6 -p-cymene)PF 3 ], [RuCl 2 (n 6 -p-cymene)PF 2 (NMe 2 )],[(r| 5 -tert-BuCp)Ru(PPh 3 )2 (CN t Bu)]BF4 , and[[(Ti 5 -MeCp)Ru(dppf)P(OCH 3 ) 3 ]BF4 ."]},{"key":"dc:title","label":"Title","values":["Utilisation of halophosphine and aminophosphine ligands in organoruthenium chemistry"]}]}],"canonical_facts":{"dc:contributor.sponsor":["University of Salford"],"dc:creator":["Boshaala, AMA"],"dc:date":["2008-03-01"],"dc:date.issued":["2008"],"dc:description.abstract":["This thesis concerns the syntheses and reactivity of areneruthenium complexescontaining halophosphine and aminophosphine ligands. Methylcyclopentadienylrutheniumchemistry is also developed together with corresponding tertbutylcyclopentadienylrutheniumchemistry. All the new compounds prepared arepseudo-octahedral with the arene or cyclopentadienyl ligand being facially coordinated.The first chapter contains a literature review of the chemistry of the rutheniumcomplex [RuCl 2(r| 6 -/?-cymene)] 2 , which is one of our starting materials. The chemistryof the ligands tris(dimethylamino)phosphine, trifluorophosphine, trichlorophosphine,tribromophosphine, dimethylaminodifluorophosphine and tert-butyldichlorophosphineis also detailed.The second chapter reports the syntheses and reactivity of the neutral compounds[RuX 2 (r| 6-/>cymene)P(NMe 2 ) 3 ] (X= Cl, Br, and I) and the cationic tris-(dimethylamino)phosphine complexes [RuCl(r| 6 -/?-cymene)P(NMe2 ) 3 (L)] (L = CO,CN'Bu, PPh3 , P(OPh3 ) 3 , P(OCH 3 ) 3 SMe 2 ). The new complexes were characterized bymultinuclear N.M.R spectroscopy; x-ray crystallographic structure determinations werecarried out on [RuCl2 (r) 6-/?-cymene)P(NMe 2 ) 3 ], [RuI 2 (r| 6 -/>-cymene)P(NMe 2 ) 3 ],[RuCl(nVcymene)P(NMe2 ) 3 (CO)]PF 6 , [RuCl(Ti 6 -p-cymene)P(NMe 2 ) 3 S(CH 3 ) 2 ]PF 6 .and [RuCl 2 (n 6 -/7-cymene)(HNMe 2 )].The third chapter describes the syntheses and reactivity of [RuX 2 (r| 6 -pcymene)P(Z) 3 ] (X= Cl, Br, and I, Z = Cl, Br. and F). The generation oftrifluorophosphine gas on a small scale is described. The observation of halogen exchange between the ruthenium centre and halophosphines is reported and the trendsin 'j(P-F) are described in the two series [RuX 2 (n 6-/>cymene)(PF 3 )] and [RuX 2 (n 6 -/?-cymene)(PF 2 {NMe 2 })].The fourth chapter contains the syntheses of two series of newalkylcyclopentadienyl complexes [(r| 5 -tert-BuCp)Ru(PPh3 )(L)Cl] and [(ry-MeCp)Ru(PPh3 )(L)Cl], (L = CO, CN'Bu, PPh 3 ) and [[(r| 5 -ter/-BuCp)Ru((L') 2 Cl] (L 1 =P(OPh 3 ) 3 , P(OCH 3 ) 3 , PPh3 , and dppm). Some hydride and cationic complexes havebeen produced from these precursors. The chapter ends with a spectroscopiccomparison of alkylcyclopentadienylruthenium derivatives.The fifth chapter contains all the experimental work carried out for chapters two,three, and fourThe sixth chapter contains suggestions for future workThe appendices contain the x-ray crystallographic metric data for nine newcompounds: [RuCl 2 (n 6 -p-cymene)P(NMe 2 ) 3 J, [RuI 2 (n 6 -p-cymene)P(NMe2 ) 3 J, [RuCl(n 6 -/7-cymene)P(NMe 2 ) 3 (CO)]PF 6 , [RuCl(r| 6 -/7-cymene)P(NMe 2 )3 S(CH 3 ) 2 ]PF 6 , [RuCl 2 (n 6 -p-cymene)(HNMe 2 )], [RuCl 2 (r| 6 -p-cymene)PF 3 ], [RuCl 2 (n 6 -p-cymene)PF 2 (NMe 2 )],[(r| 5 -tert-BuCp)Ru(PPh 3 )2 (CN t Bu)]BF4 , and[[(Ti 5 -MeCp)Ru(dppf)P(OCH 3 ) 3 ]BF4 ."],"dc:identifier":["oai:salford-repository.worktribe.com:1337252"],"dc:identifier.uri":["https://salford-repository.worktribe.com/file/1337252/1/1090980X.pdf"],"dc:language":["en"],"dc:relation.isreferencedby":["https://salford-repository.worktribe.com/output/1337252"],"dc:title":["Utilisation of halophosphine and aminophosphine ligands in organoruthenium chemistry"],"dc:type":["Thesis"],"dc:type.qualificationlevel":["Doctoral (Level 8)"]},"updated_at":"2026-07-24T04:26:09Z"}