{"id":{"repo_id":"regina","oai_identifier":"oai:uregina.scholaris.ca:10294/16400"},"canonical_url":"https://search.dev.ndltd.org/etd/regina/oai:uregina.scholaris.ca:10294/16400","repository":{"repo_id":"regina","name":"University of Regina","base_url":"https://uregina.scholaris.ca/server/oai/request"},"display":{"title":"Synthesis of ferrocenyl and 1-methylpyrrolyl bisphophines via electrophilic addition and substitution reactions of tungsten-coordinated phosphenium ions and phosphine triflates","abstract":"New symmetrical and unsymmetrical bisphosphine complexes were synthesized using electrophilic substitution reactions of tungsten pentcarbonyl-coordinated phosphenium ions [W(CO)5(PRRʹ)]+, phosphine triflates [W(CO)5{PRRʹ(OSO2CF3)}], [W(CO)5{PRCl(OSO2CF3)}] and protonated amino phosphine [W(CO)5{PCl2NH(Et)2}]+ (38) with N-methylpyrrole and ferrocene. Chloride abstractions from [W(CO)5{PPh2Cl}] (1) and [W(CO)5{PPhCl2}] (2) were carried out using aluminum chloride or silver trifluormethanesulfonate (AgOTf) to form [W(CO)5(PPh2)]+ (4), [W(CO)5{PPh2(OSO2CF3)}] (5), and [W(CO)5{PPhCl(OSO2CF3)}] (6). Trifilic acid (HOTf) was added to [W(CO)5{P(NEt)2Cl2}] (3) to form compound 38. Reactions of 4 or 5 with N-methylpyrrole led to regioisomers [W(CO)5{PPh2(2-C5H6N)}] (7) and [W(CO)5{PPh2(3-C5H6N)}] (8). Compound 6 reacted with N-methylpyrrole to form regioisomers [W(CO)5{PPhCl(2-C5H6N)}] (9) and [W(CO)5{PPhCl(3-C5H6N)}] (10). Electrophilic substitution of 4, 5, or 6 with the monosubstituted phosphine complexes 8 and 10 led to installation of another phosphino group onto the pyrrole ring to form 2,4-bis(phosphino)N-methylpyrrole complexes [(CO)10W2{μ-2,4-C5H5N)(PPh2)2}] (11), [W2(CO)10{μ-2,4-C5H5N(PPhCl)(PPh2)}] (12), and [W2(CO)10{μ-2,4-(PClPh)2C5H5N}] (26). Chloride abstractions from 12 and 26 using AgOTf led to [W2(CO)10{μ-C5H5N(PPh2)(PPhOSO2CF3)}] (13) and [W2(CO)10{μ-C5H5N(P(Ph)OTf)2}] (27). Electrophilic substitutions of 13 and 27 with H-R led to bisphosphines [W2(CO)10{μ-2-(PPh2)-4-(PPhR)C5H5N}] and [W2(CO)10{μ-C5H5N(PPhR)2}] (R = allyl, phenylalkynyl). Compound 26 was converted to the monotriflate complex [W2(CO)10{μ-2-(PPh(OSO2CF3)-4-(PClPh)C5H5N}] (28) using one equivalent of AgOTf. Addition of H-R to 28 led to monosubstituted products [W2(CO)10{μ-2-(PPhR)-4-(PClPh)C5H5N}] (R = allyl or phenylalkynyl). Chloride abstraction from monosubstituted bisphosphines with AgOTf led to [W2(CO)10{μ-2-(PPhR)-4-(PPh(OSO2CF3))C5H5N}] (R = allyl or phenylalkynyl). Addition of H-R led to [W2(CO)10{μ-2- (PPhR)-4-(PPhRʹ)C5H5N}] (R = allyl; Rʹ = phenylalkynyl or R = phenylalkynyl; Rʹ = allyl). Electrophilic addition reactions were used to install two diphenylphosphino groups onto ferrocene. Addition of 4 or 5 to [W(CO)5(PPh2(C10H9Fe)] (39) led to the known complex [(CO)10W2{μ-C10H8Fe(PPh2)2}] (40). Alternately, 2 equivalents of compound 5 or 4 were added to ferrocene to form 40. Electrophilic addition of 6 to 39 led to the unsymmetrical bisphosphine complex [W2(OC)10{μ-C10H8Fe(PPhCl)(PPh2)}] (41). Addition of 2 equivalents of 6 to ferrocene led to [W2(CO)10{μ-C10H8Fe(PPhCl)2}] (46). Chloride abstraction from 41 and 46 using silver triflate led to [W2(OC)10{μ-C10H8Fe(PPh(OSO2CF3))(PPh2)}] (42) and [W2(CO)10{μ-C10H8Fe(PPh(OSO2CF3))2}] (47). Reactions of 42 and 47 with nucleophiles H-R led to mono and disubstituted bisphosphine complexes [W2(OC)10{μ-C10H8Fe(PPhR)(PPh2)}] and [W2(OC)10{μ-C10H8Fe(PPh(R))2}] (R = allyl, phenylalkynyl, ferrocenyl). Sequential addition of two different groups to phosphorus was done by abstracting chloride from 46 using AgOTf to form [W2(CO)10{μ-C10H8Fe(PPhCl)(PPh(OSO2CF3f)}] (48). Reaction of 48 with H-R led to monosubstituted bisphosphine complex [W2(CO)10{μ-C10H8Fe(PPhCl)(PPh(R)}] (R = allyl, phenylalkynyl, ferrocenyl). Chloride abstraction from monosubstituted bisphosphines using AgOTf formed triflate complexes [W2(CO)10{μ-C10H8Fe(PPh(OSO2CF3))(PPh(R)}] (R = allyl, phenylalkynyl, ferrocenyl). Addition of H-R led to [W2(CO)10{μ-C10H8Fe(PPh(Rʹ))(PPh(R)}] (R = allyl; Rʹ = phenylalkynyl). Addition of 1/2 an equivalent of ferrocene to 38 led to [W2(CO)10{μ-C10H8Fe(PCl2)2}] (55). Compound 55 was converted into [W2(CO)10{μ-C10H8Fe(P(OTf)2(PCl(OTf))}] (56) by addition of AgOTf. Addition of H-R led to tetra-substituted products [W2(CO)10{μ-C10H8Fe(P(R)2)2}] (R = allyl, phenylakynyl, and indolyl).","abstract_html":"New symmetrical and unsymmetrical bisphosphine complexes were synthesized using electrophilic substitution reactions of tungsten pentcarbonyl-coordinated phosphenium ions [W(CO)5(PRRʹ)]+, phosphine triflates [W(CO)5{PRRʹ(OSO2CF3)}], [W(CO)5{PRCl(OSO2CF3)}] and protonated amino phosphine [W(CO)5{PCl2NH(Et)2}]+ (38) with N-methylpyrrole and ferrocene. Chloride abstractions from [W(CO)5{PPh2Cl}] (1) and [W(CO)5{PPhCl2}] (2) were carried out using aluminum chloride or silver trifluormethanesulfonate (AgOTf) to form [W(CO)5(PPh2)]+ (4), [W(CO)5{PPh2(OSO2CF3)}] (5), and [W(CO)5{PPhCl(OSO2CF3)}] (6). Trifilic acid (HOTf) was added to [W(CO)5{P(NEt)2Cl2}] (3) to form compound 38. Reactions of 4 or 5 with N-methylpyrrole led to regioisomers [W(CO)5{PPh2(2-C5H6N)}] (7) and [W(CO)5{PPh2(3-C5H6N)}] (8). Compound 6 reacted with N-methylpyrrole to form regioisomers [W(CO)5{PPhCl(2-C5H6N)}] (9) and [W(CO)5{PPhCl(3-C5H6N)}] (10). Electrophilic substitution of 4, 5, or 6 with the monosubstituted phosphine complexes 8 and 10 led to installation of another phosphino group onto the pyrrole ring to form 2,4-bis(phosphino)N-methylpyrrole complexes [(CO)10W2{μ-2,4-C5H5N)(PPh2)2}] (11), [W2(CO)10{μ-2,4-C5H5N(PPhCl)(PPh2)}] (12), and [W2(CO)10{μ-2,4-(PClPh)2C5H5N}] (26). Chloride abstractions from 12 and 26 using AgOTf led to [W2(CO)10{μ-C5H5N(PPh2)(PPhOSO2CF3)}] (13) and [W2(CO)10{μ-C5H5N(P(Ph)OTf)2}] (27). Electrophilic substitutions of 13 and 27 with H-R led to bisphosphines [W2(CO)10{μ-2-(PPh2)-4-(PPhR)C5H5N}] and [W2(CO)10{μ-C5H5N(PPhR)2}] (R = allyl, phenylalkynyl). Compound 26 was converted to the monotriflate complex [W2(CO)10{μ-2-(PPh(OSO2CF3)-4-(PClPh)C5H5N}] (28) using one equivalent of AgOTf. Addition of H-R to 28 led to monosubstituted products [W2(CO)10{μ-2-(PPhR)-4-(PClPh)C5H5N}] (R = allyl or phenylalkynyl). Chloride abstraction from monosubstituted bisphosphines with AgOTf led to [W2(CO)10{μ-2-(PPhR)-4-(PPh(OSO2CF3))C5H5N}] (R = allyl or phenylalkynyl). Addition of H-R led to [W2(CO)10{μ-2- (PPhR)-4-(PPhRʹ)C5H5N}] (R = allyl; Rʹ = phenylalkynyl or R = phenylalkynyl; Rʹ = allyl). Electrophilic addition reactions were used to install two diphenylphosphino groups onto ferrocene. Addition of 4 or 5 to [W(CO)5(PPh2(C10H9Fe)] (39) led to the known complex [(CO)10W2{μ-C10H8Fe(PPh2)2}] (40). Alternately, 2 equivalents of compound 5 or 4 were added to ferrocene to form 40. Electrophilic addition of 6 to 39 led to the unsymmetrical bisphosphine complex [W2(OC)10{μ-C10H8Fe(PPhCl)(PPh2)}] (41). Addition of 2 equivalents of 6 to ferrocene led to [W2(CO)10{μ-C10H8Fe(PPhCl)2}] (46). Chloride abstraction from 41 and 46 using silver triflate led to [W2(OC)10{μ-C10H8Fe(PPh(OSO2CF3))(PPh2)}] (42) and [W2(CO)10{μ-C10H8Fe(PPh(OSO2CF3))2}] (47). Reactions of 42 and 47 with nucleophiles H-R led to mono and disubstituted bisphosphine complexes [W2(OC)10{μ-C10H8Fe(PPhR)(PPh2)}] and [W2(OC)10{μ-C10H8Fe(PPh(R))2}] (R = allyl, phenylalkynyl, ferrocenyl). Sequential addition of two different groups to phosphorus was done by abstracting chloride from 46 using AgOTf to form [W2(CO)10{μ-C10H8Fe(PPhCl)(PPh(OSO2CF3f)}] (48). Reaction of 48 with H-R led to monosubstituted bisphosphine complex [W2(CO)10{μ-C10H8Fe(PPhCl)(PPh(R)}] (R = allyl, phenylalkynyl, ferrocenyl). Chloride abstraction from monosubstituted bisphosphines using AgOTf formed triflate complexes [W2(CO)10{μ-C10H8Fe(PPh(OSO2CF3))(PPh(R)}] (R = allyl, phenylalkynyl, ferrocenyl). Addition of H-R led to [W2(CO)10{μ-C10H8Fe(PPh(Rʹ))(PPh(R)}] (R = allyl; Rʹ = phenylalkynyl). Addition of 1/2 an equivalent of ferrocene to 38 led to [W2(CO)10{μ-C10H8Fe(PCl2)2}] (55). Compound 55 was converted into [W2(CO)10{μ-C10H8Fe(P(OTf)2(PCl(OTf))}] (56) by addition of AgOTf. Addition of H-R led to tetra-substituted products [W2(CO)10{μ-C10H8Fe(P(R)2)2}] (R = allyl, phenylakynyl, and indolyl).","abstract_has_math":false,"creators":["Bumraiwha, Hamdi F K"],"institution":"Faculty of Graduate Studies and Research, University of Regina","degree_name":"Doctor of Philosophy (PhD)","degree_level":null,"degree_discipline":"Chemistry","degree_department":null,"school":null,"contributors":[],"advisors":["Sterenberg, Brian"],"committee_chairs":[],"committee_members":["Mihichuk, Lynn","Murphy, Scott","Zeng, Fanhua (Bill)"],"year":2023,"date_issued":"2023-08","date_published":"2023-08","updated_at":"2026-07-24T04:03:34Z","subjects":[],"languages":["en"],"rights":[],"rights_urls":[],"identifier_entries":[{"key":"dc:identifier.doi","label":"DOI","values":["https://doi.org/10.82465/4197"],"render_values":[{"text":"https://doi.org/10.82465/4197","href":"https://doi.org/10.82465/4197","code":true}]}]},"links":{"outbound_url":"https://hdl.handle.net/10294/16400","outbound_label":"Handle","outbound_source":"dc:identifier.uri"},"metadata_groups":[{"id":"people","label":"People","entries":[{"key":"dc:contributor.advisor","label":"Advisor","values":["Sterenberg, Brian"]},{"key":"dc:contributor.committeemember","label":"Committee Member","values":["Mihichuk, Lynn","Murphy, Scott","Zeng, Fanhua (Bill)"]},{"key":"dc:creator","label":"Author","values":["Bumraiwha, Hamdi F K"]}]},{"id":"academic_context","label":"Academic Context","entries":[{"key":"dc:date.accessioned","label":"Dc Date Accessioned","values":["2024-10-11T16:50:46Z"]},{"key":"dc:date.available","label":"Dc Date Available","values":["2024-10-11T16:50:46Z"]},{"key":"dc:date.issued","label":"Date","values":["2023-08"]},{"key":"dc:publisher","label":"Institution","values":["Faculty of Graduate Studies and Research, University of Regina"]},{"key":"dc:type","label":"Dc Type","values":["master thesis"]},{"key":"thesis:degree_discipline","label":"Discipline","values":["Chemistry"]},{"key":"thesis:degree_name","label":"Degree Name","values":["Doctor of Philosophy (PhD)"]},{"key":"thesis:institution_name","label":"Thesis Institution Name","values":["Faculty of Graduate Studies and Research, University of Regina"]}]},{"id":"language_rights","label":"Language and Rights","entries":[{"key":"dc:language.iso","label":"Language (ISO)","values":["en"]}]},{"id":"identifiers","label":"Identifiers","entries":[{"key":"dc:identifier.doi","label":"DOI","values":["https://doi.org/10.82465/4197"]},{"key":"dc:identifier.uri","label":"Identifier URI","values":["https://hdl.handle.net/10294/16400"]}]},{"id":"additional","label":"Additional Metadata","entries":[{"key":"dc:description","label":"Description","values":["A Thesis Submitted to the Faculty of Graduate Studies and Research In Partial Fulfillment of the Requirements for the Degree of Doctor of Philosophy in Chemistry, University of Regina. xviii, 160 p."]},{"key":"dc:description.abstract","label":"Abstract","values":["New symmetrical and unsymmetrical bisphosphine complexes were synthesized using electrophilic substitution reactions of tungsten pentcarbonyl-coordinated phosphenium ions [W(CO)5(PRRʹ)]+, phosphine triflates [W(CO)5{PRRʹ(OSO2CF3)}], [W(CO)5{PRCl(OSO2CF3)}] and protonated amino phosphine [W(CO)5{PCl2NH(Et)2}]+ (38) with N-methylpyrrole and ferrocene. Chloride abstractions from [W(CO)5{PPh2Cl}] (1) and [W(CO)5{PPhCl2}] (2) were carried out using aluminum chloride or silver trifluormethanesulfonate (AgOTf) to form [W(CO)5(PPh2)]+ (4), [W(CO)5{PPh2(OSO2CF3)}] (5), and [W(CO)5{PPhCl(OSO2CF3)}] (6). Trifilic acid (HOTf) was added to [W(CO)5{P(NEt)2Cl2}] (3) to form compound 38. Reactions of 4 or 5 with N-methylpyrrole led to regioisomers [W(CO)5{PPh2(2-C5H6N)}] (7) and [W(CO)5{PPh2(3-C5H6N)}] (8). Compound 6 reacted with N-methylpyrrole to form regioisomers [W(CO)5{PPhCl(2-C5H6N)}] (9) and [W(CO)5{PPhCl(3-C5H6N)}] (10). Electrophilic substitution of 4, 5, or 6 with the monosubstituted phosphine complexes 8 and 10 led to installation of another phosphino group onto the pyrrole ring to form 2,4-bis(phosphino)N-methylpyrrole complexes [(CO)10W2{μ-2,4-C5H5N)(PPh2)2}] (11), [W2(CO)10{μ-2,4-C5H5N(PPhCl)(PPh2)}] (12), and [W2(CO)10{μ-2,4-(PClPh)2C5H5N}] (26). Chloride abstractions from 12 and 26 using AgOTf led to [W2(CO)10{μ-C5H5N(PPh2)(PPhOSO2CF3)}] (13) and [W2(CO)10{μ-C5H5N(P(Ph)OTf)2}] (27). Electrophilic substitutions of 13 and 27 with H-R led to bisphosphines [W2(CO)10{μ-2-(PPh2)-4-(PPhR)C5H5N}] and [W2(CO)10{μ-C5H5N(PPhR)2}] (R = allyl, phenylalkynyl). Compound 26 was converted to the monotriflate complex [W2(CO)10{μ-2-(PPh(OSO2CF3)-4-(PClPh)C5H5N}] (28) using one equivalent of AgOTf. Addition of H-R to 28 led to monosubstituted products [W2(CO)10{μ-2-(PPhR)-4-(PClPh)C5H5N}] (R = allyl or phenylalkynyl). Chloride abstraction from monosubstituted bisphosphines with AgOTf led to [W2(CO)10{μ-2-(PPhR)-4-(PPh(OSO2CF3))C5H5N}] (R = allyl or phenylalkynyl). Addition of H-R led to [W2(CO)10{μ-2- (PPhR)-4-(PPhRʹ)C5H5N}] (R = allyl; Rʹ = phenylalkynyl or R = phenylalkynyl; Rʹ = allyl). Electrophilic addition reactions were used to install two diphenylphosphino groups onto ferrocene. Addition of 4 or 5 to [W(CO)5(PPh2(C10H9Fe)] (39) led to the known complex [(CO)10W2{μ-C10H8Fe(PPh2)2}] (40). Alternately, 2 equivalents of compound 5 or 4 were added to ferrocene to form 40. Electrophilic addition of 6 to 39 led to the unsymmetrical bisphosphine complex [W2(OC)10{μ-C10H8Fe(PPhCl)(PPh2)}] (41). Addition of 2 equivalents of 6 to ferrocene led to [W2(CO)10{μ-C10H8Fe(PPhCl)2}] (46). Chloride abstraction from 41 and 46 using silver triflate led to [W2(OC)10{μ-C10H8Fe(PPh(OSO2CF3))(PPh2)}] (42) and [W2(CO)10{μ-C10H8Fe(PPh(OSO2CF3))2}] (47). Reactions of 42 and 47 with nucleophiles H-R led to mono and disubstituted bisphosphine complexes [W2(OC)10{μ-C10H8Fe(PPhR)(PPh2)}] and [W2(OC)10{μ-C10H8Fe(PPh(R))2}] (R = allyl, phenylalkynyl, ferrocenyl). Sequential addition of two different groups to phosphorus was done by abstracting chloride from 46 using AgOTf to form [W2(CO)10{μ-C10H8Fe(PPhCl)(PPh(OSO2CF3f)}] (48). Reaction of 48 with H-R led to monosubstituted bisphosphine complex [W2(CO)10{μ-C10H8Fe(PPhCl)(PPh(R)}] (R = allyl, phenylalkynyl, ferrocenyl). Chloride abstraction from monosubstituted bisphosphines using AgOTf formed triflate complexes [W2(CO)10{μ-C10H8Fe(PPh(OSO2CF3))(PPh(R)}] (R = allyl, phenylalkynyl, ferrocenyl). Addition of H-R led to [W2(CO)10{μ-C10H8Fe(PPh(Rʹ))(PPh(R)}] (R = allyl; Rʹ = phenylalkynyl). Addition of 1/2 an equivalent of ferrocene to 38 led to [W2(CO)10{μ-C10H8Fe(PCl2)2}] (55). Compound 55 was converted into [W2(CO)10{μ-C10H8Fe(P(OTf)2(PCl(OTf))}] (56) by addition of AgOTf. Addition of H-R led to tetra-substituted products [W2(CO)10{μ-C10H8Fe(P(R)2)2}] (R = allyl, phenylakynyl, and indolyl)."]},{"key":"dc:title","label":"Title","values":["Synthesis of ferrocenyl and 1-methylpyrrolyl bisphophines via electrophilic addition and substitution reactions of tungsten-coordinated phosphenium ions and phosphine triflates"]}]}],"canonical_facts":{"dc:contributor.advisor":["Sterenberg, Brian"],"dc:contributor.committeemember":["Mihichuk, Lynn","Murphy, Scott","Zeng, Fanhua (Bill)"],"dc:creator":["Bumraiwha, Hamdi F K"],"dc:date.accessioned":["2024-10-11T16:50:46Z"],"dc:date.available":["2024-10-11T16:50:46Z"],"dc:date.issued":["2023-08"],"dc:description":["A Thesis Submitted to the Faculty of Graduate Studies and Research In Partial Fulfillment of the Requirements for the Degree of Doctor of Philosophy in Chemistry, University of Regina. xviii, 160 p."],"dc:description.abstract":["New symmetrical and unsymmetrical bisphosphine complexes were synthesized using electrophilic substitution reactions of tungsten pentcarbonyl-coordinated phosphenium ions [W(CO)5(PRRʹ)]+, phosphine triflates [W(CO)5{PRRʹ(OSO2CF3)}], [W(CO)5{PRCl(OSO2CF3)}] and protonated amino phosphine [W(CO)5{PCl2NH(Et)2}]+ (38) with N-methylpyrrole and ferrocene. Chloride abstractions from [W(CO)5{PPh2Cl}] (1) and [W(CO)5{PPhCl2}] (2) were carried out using aluminum chloride or silver trifluormethanesulfonate (AgOTf) to form [W(CO)5(PPh2)]+ (4), [W(CO)5{PPh2(OSO2CF3)}] (5), and [W(CO)5{PPhCl(OSO2CF3)}] (6). Trifilic acid (HOTf) was added to [W(CO)5{P(NEt)2Cl2}] (3) to form compound 38. Reactions of 4 or 5 with N-methylpyrrole led to regioisomers [W(CO)5{PPh2(2-C5H6N)}] (7) and [W(CO)5{PPh2(3-C5H6N)}] (8). Compound 6 reacted with N-methylpyrrole to form regioisomers [W(CO)5{PPhCl(2-C5H6N)}] (9) and [W(CO)5{PPhCl(3-C5H6N)}] (10). Electrophilic substitution of 4, 5, or 6 with the monosubstituted phosphine complexes 8 and 10 led to installation of another phosphino group onto the pyrrole ring to form 2,4-bis(phosphino)N-methylpyrrole complexes [(CO)10W2{μ-2,4-C5H5N)(PPh2)2}] (11), [W2(CO)10{μ-2,4-C5H5N(PPhCl)(PPh2)}] (12), and [W2(CO)10{μ-2,4-(PClPh)2C5H5N}] (26). Chloride abstractions from 12 and 26 using AgOTf led to [W2(CO)10{μ-C5H5N(PPh2)(PPhOSO2CF3)}] (13) and [W2(CO)10{μ-C5H5N(P(Ph)OTf)2}] (27). Electrophilic substitutions of 13 and 27 with H-R led to bisphosphines [W2(CO)10{μ-2-(PPh2)-4-(PPhR)C5H5N}] and [W2(CO)10{μ-C5H5N(PPhR)2}] (R = allyl, phenylalkynyl). Compound 26 was converted to the monotriflate complex [W2(CO)10{μ-2-(PPh(OSO2CF3)-4-(PClPh)C5H5N}] (28) using one equivalent of AgOTf. Addition of H-R to 28 led to monosubstituted products [W2(CO)10{μ-2-(PPhR)-4-(PClPh)C5H5N}] (R = allyl or phenylalkynyl). Chloride abstraction from monosubstituted bisphosphines with AgOTf led to [W2(CO)10{μ-2-(PPhR)-4-(PPh(OSO2CF3))C5H5N}] (R = allyl or phenylalkynyl). Addition of H-R led to [W2(CO)10{μ-2- (PPhR)-4-(PPhRʹ)C5H5N}] (R = allyl; Rʹ = phenylalkynyl or R = phenylalkynyl; Rʹ = allyl). Electrophilic addition reactions were used to install two diphenylphosphino groups onto ferrocene. Addition of 4 or 5 to [W(CO)5(PPh2(C10H9Fe)] (39) led to the known complex [(CO)10W2{μ-C10H8Fe(PPh2)2}] (40). Alternately, 2 equivalents of compound 5 or 4 were added to ferrocene to form 40. Electrophilic addition of 6 to 39 led to the unsymmetrical bisphosphine complex [W2(OC)10{μ-C10H8Fe(PPhCl)(PPh2)}] (41). Addition of 2 equivalents of 6 to ferrocene led to [W2(CO)10{μ-C10H8Fe(PPhCl)2}] (46). Chloride abstraction from 41 and 46 using silver triflate led to [W2(OC)10{μ-C10H8Fe(PPh(OSO2CF3))(PPh2)}] (42) and [W2(CO)10{μ-C10H8Fe(PPh(OSO2CF3))2}] (47). Reactions of 42 and 47 with nucleophiles H-R led to mono and disubstituted bisphosphine complexes [W2(OC)10{μ-C10H8Fe(PPhR)(PPh2)}] and [W2(OC)10{μ-C10H8Fe(PPh(R))2}] (R = allyl, phenylalkynyl, ferrocenyl). Sequential addition of two different groups to phosphorus was done by abstracting chloride from 46 using AgOTf to form [W2(CO)10{μ-C10H8Fe(PPhCl)(PPh(OSO2CF3f)}] (48). Reaction of 48 with H-R led to monosubstituted bisphosphine complex [W2(CO)10{μ-C10H8Fe(PPhCl)(PPh(R)}] (R = allyl, phenylalkynyl, ferrocenyl). Chloride abstraction from monosubstituted bisphosphines using AgOTf formed triflate complexes [W2(CO)10{μ-C10H8Fe(PPh(OSO2CF3))(PPh(R)}] (R = allyl, phenylalkynyl, ferrocenyl). Addition of H-R led to [W2(CO)10{μ-C10H8Fe(PPh(Rʹ))(PPh(R)}] (R = allyl; Rʹ = phenylalkynyl). Addition of 1/2 an equivalent of ferrocene to 38 led to [W2(CO)10{μ-C10H8Fe(PCl2)2}] (55). Compound 55 was converted into [W2(CO)10{μ-C10H8Fe(P(OTf)2(PCl(OTf))}] (56) by addition of AgOTf. Addition of H-R led to tetra-substituted products [W2(CO)10{μ-C10H8Fe(P(R)2)2}] (R = allyl, phenylakynyl, and indolyl)."],"dc:identifier.doi":["https://doi.org/10.82465/4197"],"dc:identifier.uri":["https://hdl.handle.net/10294/16400"],"dc:language.iso":["en"],"dc:publisher":["Faculty of Graduate Studies and Research, University of Regina"],"dc:title":["Synthesis of ferrocenyl and 1-methylpyrrolyl bisphophines via electrophilic addition and substitution reactions of tungsten-coordinated phosphenium ions and phosphine triflates"],"dc:type":["master thesis"],"thesis:degree_discipline":["Chemistry"],"thesis:degree_name":["Doctor of Philosophy (PhD)"],"thesis:institution_name":["Faculty of Graduate Studies and Research, University of Regina"]},"updated_at":"2026-07-24T04:03:34Z"}