FRINK Linked Data Fragments server

Matches in SemOpenAlex for { <https://semopenalex.org/work/W2248871462> ?p ?o ?g. }

• W2248871462 abstract "A new series of aminomethylphosphine ligands incorporating a PCN backbone and a pendant amine were synthesised using a phosphorus Mannich condensation reaction. Their coordination capabilities were investigated with late transition metal centres. Following a procedure well established within our research group, several phosphines were obtained using {P(CH2OH)4}Cl (THPC) in two steps. Firstly, THPC was reacted with various ortho and para anilines to give phosphonium salts P{CH2N(H)R}4Cl (R = C6H5, o–MeC6H4, o– i PrC6H4, o–t BuC6H4, o–FC6H4, o–CF3C6H4, o–{C(Me)=CH2}C6H4, p–MeC6H4, p–i PrC6H4, p–FC6H4 and p–EtC6H4). Secondly, these new salts were reacted with Et3N to obtain the cyclic RN(H)CH2P{(CH2)3(NR)2} phosphines (R = para–substituted anilines) or with KOt Bu to obtain acyclic P{CH2N(H)R}3 phosphines (R = ortho-substituted anilines) and cyclic P{CH2N(R)CH2}2P diphosphines (R = ortho–substituted anilines). Double condensation was observed in the 31P{1 H} NMR of cyclic phosphines RN(H)CH2P{(CH2)3(NR)2} to form {(CH2)3(NR)2}PCH2N(R)CH2P{(CH2)3(NR)2} diphosphines. Some cyclic phosphines were investigated under a wide range of conditions with Ph2PCH2OH giving asymmetric Ph2PCH2N(R)CH2P{(CH2)3(NR)2} diphosphines along with symmetric diphosphines counterparts and other phosphorus coproducts according to 31P{1 H} NMR and MS. A novel bicyclic OP{CH2N(R)CH2}3PO diphosphine (R = p–MeC6H4) was obtained as crystalline solid from the filtrate of the reaction between RN(H)CH2P{(CH2)3(NR)2} and Ph2PCH2OH and it was characterised by X–ray spectroscopy. Attempts to synthesise this diphosphine from P(CH2OH)3 and p–MeC6H4 were unsuccessful. The family of aminomethylphosphine ligands was extended by treating Ph2PCH2OH or CgPCH2OH (Cg = 1,3,5,7–tetramethyl–2,4,8–trioxa–6–phosphaadamantane) with various primary amines to afford R(H)NCH2PR’2 (R’ = Cg or Ph). Symmetric Ph2PCH2N(R)CH2Ph2 diphosphines were observed in the 31P{1 H} NMR spectra indicating that phosphines with Ph2P– moiety were more susceptible to undertake a second condensation. Novel asymmetric o–{Ph2PCH2C(H)(CH3)}C6H4N(H)CH2PPh2 diphosphine was synthesised by treatment of o-{C(Me)=CH2}C6H4NH2 with Ph2PH to afford o– {Ph2PCH2C(H)(CH3)}C6H4NH2 followed by condensation of the amino group with Ph2PCH2OH. Analogous o–{CgPCH2C(H)(CH3)}C6H4NH2 phosphine was also obtained. The coordination capabilities of selected compounds was studied with late transition metal precursor such as Pt(II), Pd(II) and Ru(II). Monophosphine compounds acted as Pmonodentate ligands to form square planar cis and trans MCl2L2 (M = Pt and Pd) complexes. However, whereas cyclic ligands RN(H)CH2P{(CH2)3(NR)2} afforded cisMCl2L2, acyclic ligands P{CH2N(H)R}3 afforded trans-MCl2L2 along with cis-PtCl2L2 in some cases. Those phosphines which conducted double condensation adopted a P,Pchelate mode to form a 6–membered M–P–C–N–C–P to afford cis-MCl2L (M = Pt and Pd). More interesting is the rarely observed P,P-bridging mode exhibited by P{CH2N(R)CH2}2P ligands to form homobimetallic cis–(PtCl2L)2 complexes and {RhCl2(η5 –Cp*)}2L complexes. These metal compounds were obtained and characterised by in situ NMR however their structures were further supported by simulated 31P{1 H} NMR and X–ray studies. Asymmetric Ph2PCH2N(R)CH2P{(CH2)3(NR)2} diphosphines coordinated to Pt(II) in a P,P–chelate fashion affording a mixture of cis and trans bis(chelate) (PtL2)Cl2. Complex in trans geometry was isolated and the structure was further supported by X–ray crystallography. The coordination capabilities of the ligands were investigated with Ru(II) metal centre revealing “piano–stool” structure of the type RuCl2(η6 –p–cymene)L where the monophosphines adopted a P-monodentate mode and {RuCl2(η6 –p–cymene)}2L where the diphosphines adopted a P,P-bridging mode. Preliminary studies with selected Ru complexes were carried out to investigate their potential catalytic activity to trap CO2 by its insertion into the Ru–Cl bond which suggested that the chloride needs to be substituted by a hydride prior the CO2 insertion. Compounds were characterised by spectroscopic techniques and the structure of some phosphines was further supported by X–ray crystallography." @default.
• W2248871462 created "2016-06-24" @default.
• W2248871462 creator A5061544960 @default.
• W2248871462 date "2015-01-01" @default.
• W2248871462 modified "2023-09-24" @default.
• W2248871462 title "Synthesis of novel aminomethylphosphine complexes" @default.
• W2248871462 hasPublicationYear "2015" @default.
• W2248871462 type Work @default.
• W2248871462 sameAs 2248871462 @default.
• W2248871462 citedByCount "0" @default.
• W2248871462 crossrefType "dissertation" @default.
• W2248871462 hasAuthorship W2248871462A5061544960 @default.
• W2248871462 hasConcept C131779359 @default.
• W2248871462 hasConcept C155647269 @default.
• W2248871462 hasConcept C161790260 @default.
• W2248871462 hasConcept C178790620 @default.
• W2248871462 hasConcept C185592680 @default.
• W2248871462 hasConcept C188027245 @default.
• W2248871462 hasConcept C2775904426 @default.
• W2248871462 hasConcept C2778818089 @default.
• W2248871462 hasConcept C2780707935 @default.
• W2248871462 hasConcept C510538283 @default.
• W2248871462 hasConcept C71240020 @default.
• W2248871462 hasConceptScore W2248871462C131779359 @default.
• W2248871462 hasConceptScore W2248871462C155647269 @default.
• W2248871462 hasConceptScore W2248871462C161790260 @default.
• W2248871462 hasConceptScore W2248871462C178790620 @default.
• W2248871462 hasConceptScore W2248871462C185592680 @default.
• W2248871462 hasConceptScore W2248871462C188027245 @default.
• W2248871462 hasConceptScore W2248871462C2775904426 @default.
• W2248871462 hasConceptScore W2248871462C2778818089 @default.
• W2248871462 hasConceptScore W2248871462C2780707935 @default.
• W2248871462 hasConceptScore W2248871462C510538283 @default.
• W2248871462 hasConceptScore W2248871462C71240020 @default.
• W2248871462 hasLocation W22488714621 @default.
• W2248871462 hasOpenAccess W2248871462 @default.
• W2248871462 hasPrimaryLocation W22488714621 @default.
• W2248871462 hasRelatedWork W1981738464 @default.
• W2248871462 hasRelatedWork W2005045895 @default.
• W2248871462 hasRelatedWork W2005252491 @default.
• W2248871462 hasRelatedWork W2026201389 @default.
• W2248871462 hasRelatedWork W2035409838 @default.
• W2248871462 hasRelatedWork W2038352001 @default.
• W2248871462 hasRelatedWork W2041144870 @default.
• W2248871462 hasRelatedWork W2053993974 @default.
• W2248871462 hasRelatedWork W2065442818 @default.
• W2248871462 hasRelatedWork W2073068390 @default.
• W2248871462 hasRelatedWork W2075924280 @default.
• W2248871462 hasRelatedWork W2077037796 @default.
• W2248871462 hasRelatedWork W2282509534 @default.
• W2248871462 hasRelatedWork W2325397456 @default.
• W2248871462 hasRelatedWork W2330833042 @default.
• W2248871462 hasRelatedWork W2473577735 @default.
• W2248871462 hasRelatedWork W3115935217 @default.
• W2248871462 hasRelatedWork W3183334042 @default.
• W2248871462 hasRelatedWork W3212683320 @default.
• W2248871462 hasRelatedWork W2026862131 @default.
• W2248871462 isParatext "false" @default.
• W2248871462 isRetracted "false" @default.
• W2248871462 magId "2248871462" @default.
• W2248871462 workType "dissertation" @default.