Synthesis of ferrocenyl and 1-methylpyrrolyl bisphophines via electrophilic addition and substitution reactions of tungsten-coordinated phosphenium ions and phosphine triflates
type: CreativeWork
description: 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 …
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 …
author: Bumraiwha, Hamdi F K
language: en
date published: 2023-08
date modified: 2026-07-24T04:03:34Z
provider: University of Regina
publisher: Networked Digital Library of Theses and Dissertations
type: WebPage
source organization: Faculty of Graduate Studies and Research, University of Regina

PropertyValue
property ID: Handle
value: https://hdl.handle.net/10294/16400

PropertyValue
property ID: DOI
value: 10.82465/4197