Synthesis of novel heterocyclic P-ligands and their application in transition metal complexes

G. Keglevich, Andrea Kerényi, T. Körtvélyesi

Research output: Chapter in Book/Report/Conference proceedingChapter

3 Citations (Scopus)

Abstract

2,4,6-Trialkylphenyl-1H-phospholes of certain extent of aromaticity displayed a special reactivity towards dichlorodibenzonitrileplatinum and gave a mixture of a monophosphole complex and a trans bis(phosphole) complex on reaction with the complexant. The 1H-phosphole 2H-phosphole sigmatropic rearrangement was utilised in the preparation of new P-ligands. A variety of 2,5-dihydro-1H-phosphole oxides were converted to 3-phosphabicyclo[3.1.0]hexane 3-oxides, 1,2-dihydrophosphinine oxides and 4-dichloromethylene-1,4-dihydrophosphinine oxides that after deoxygenation with silanes served as P-ligands in rhodium and palladium complexes. New phosphinine derivatives with exocyclic P-functions were developed by the Michael-addition of diphenylphosphine oxide to 1-phenyl-1,2-dihydrophosphinine oxide and by the double deoxygenation of the 1,2,3,6-tetrahydrophosphinine oxide so obtained. The bis(phosphine) was converted to a cis chelate complex by reaction with PtCl2(NCPh)2. The related phosphinoxido-hexahydrophospinine oxide was taken in a similar sequence of reactions. Dibenzo[c.e][1,2]oxaphosphorines with a variety of P-substituents were also synthesized and used in complexations. In the first place, aryl-dibenzooxaphosporines were made available and than converted to the platinum complexes containing only one heterocyclic unit. Then a few P-alkoxy and P-amino dibenzooxaphosphorines including optically active derivatives were prepared and transformed to the corresponding platinum complexes that, in this particular case, contained two heterocyclic P-ligands in positioncis. Ring opening reaction accompanying the substitution of the starting chlorodibenzooxaphosphorine furnished a new P-ligand, 1-hydroxy-1 -diphenylphosphinobiphenyl that on reaction with the platinum precursor gave a bis(triarylphosphino) complex. The hydroxy-diphenylphosphino-biphenyl was modified by phosphorylation to furnish a special bidentate P-ligand and subsequently a ring Pt-complex. Aiming at the synthesis of further bidentate P-ligands, methylaminoethanol and L-ephedrine were reacted with two equivalents of chloro-dibenzooxaphosphorine. The resulting bis(dibenzooxaphosphorines) were utilized in the preparation of 7-ring platinum complexes.

Original languageEnglish
Title of host publicationTransition Metal Chemistry: New Research
PublisherNova Science Publishers, Inc.
Pages83-99
Number of pages17
ISBN (Print)9781604567021
Publication statusPublished - 2008

Fingerprint

transition metals
ligands
oxides
synthesis
platinum
deoxygenation
rings
phosphorylation
preparation
rhodium
chelates
phosphines
silanes
palladium
reactivity
substitutes

ASJC Scopus subject areas

  • Physics and Astronomy(all)

Cite this

Keglevich, G., Kerényi, A., & Körtvélyesi, T. (2008). Synthesis of novel heterocyclic P-ligands and their application in transition metal complexes. In Transition Metal Chemistry: New Research (pp. 83-99). Nova Science Publishers, Inc..

Synthesis of novel heterocyclic P-ligands and their application in transition metal complexes. / Keglevich, G.; Kerényi, Andrea; Körtvélyesi, T.

Transition Metal Chemistry: New Research. Nova Science Publishers, Inc., 2008. p. 83-99.

Research output: Chapter in Book/Report/Conference proceedingChapter

Keglevich, G, Kerényi, A & Körtvélyesi, T 2008, Synthesis of novel heterocyclic P-ligands and their application in transition metal complexes. in Transition Metal Chemistry: New Research. Nova Science Publishers, Inc., pp. 83-99.
Keglevich G, Kerényi A, Körtvélyesi T. Synthesis of novel heterocyclic P-ligands and their application in transition metal complexes. In Transition Metal Chemistry: New Research. Nova Science Publishers, Inc. 2008. p. 83-99
Keglevich, G. ; Kerényi, Andrea ; Körtvélyesi, T. / Synthesis of novel heterocyclic P-ligands and their application in transition metal complexes. Transition Metal Chemistry: New Research. Nova Science Publishers, Inc., 2008. pp. 83-99
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abstract = "2,4,6-Trialkylphenyl-1H-phospholes of certain extent of aromaticity displayed a special reactivity towards dichlorodibenzonitrileplatinum and gave a mixture of a monophosphole complex and a trans bis(phosphole) complex on reaction with the complexant. The 1H-phosphole 2H-phosphole sigmatropic rearrangement was utilised in the preparation of new P-ligands. A variety of 2,5-dihydro-1H-phosphole oxides were converted to 3-phosphabicyclo[3.1.0]hexane 3-oxides, 1,2-dihydrophosphinine oxides and 4-dichloromethylene-1,4-dihydrophosphinine oxides that after deoxygenation with silanes served as P-ligands in rhodium and palladium complexes. New phosphinine derivatives with exocyclic P-functions were developed by the Michael-addition of diphenylphosphine oxide to 1-phenyl-1,2-dihydrophosphinine oxide and by the double deoxygenation of the 1,2,3,6-tetrahydrophosphinine oxide so obtained. The bis(phosphine) was converted to a cis chelate complex by reaction with PtCl2(NCPh)2. The related phosphinoxido-hexahydrophospinine oxide was taken in a similar sequence of reactions. Dibenzo[c.e][1,2]oxaphosphorines with a variety of P-substituents were also synthesized and used in complexations. In the first place, aryl-dibenzooxaphosporines were made available and than converted to the platinum complexes containing only one heterocyclic unit. Then a few P-alkoxy and P-amino dibenzooxaphosphorines including optically active derivatives were prepared and transformed to the corresponding platinum complexes that, in this particular case, contained two heterocyclic P-ligands in positioncis. Ring opening reaction accompanying the substitution of the starting chlorodibenzooxaphosphorine furnished a new P-ligand, 1-hydroxy-1 -diphenylphosphinobiphenyl that on reaction with the platinum precursor gave a bis(triarylphosphino) complex. The hydroxy-diphenylphosphino-biphenyl was modified by phosphorylation to furnish a special bidentate P-ligand and subsequently a ring Pt-complex. Aiming at the synthesis of further bidentate P-ligands, methylaminoethanol and L-ephedrine were reacted with two equivalents of chloro-dibenzooxaphosphorine. The resulting bis(dibenzooxaphosphorines) were utilized in the preparation of 7-ring platinum complexes.",
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N2 - 2,4,6-Trialkylphenyl-1H-phospholes of certain extent of aromaticity displayed a special reactivity towards dichlorodibenzonitrileplatinum and gave a mixture of a monophosphole complex and a trans bis(phosphole) complex on reaction with the complexant. The 1H-phosphole 2H-phosphole sigmatropic rearrangement was utilised in the preparation of new P-ligands. A variety of 2,5-dihydro-1H-phosphole oxides were converted to 3-phosphabicyclo[3.1.0]hexane 3-oxides, 1,2-dihydrophosphinine oxides and 4-dichloromethylene-1,4-dihydrophosphinine oxides that after deoxygenation with silanes served as P-ligands in rhodium and palladium complexes. New phosphinine derivatives with exocyclic P-functions were developed by the Michael-addition of diphenylphosphine oxide to 1-phenyl-1,2-dihydrophosphinine oxide and by the double deoxygenation of the 1,2,3,6-tetrahydrophosphinine oxide so obtained. The bis(phosphine) was converted to a cis chelate complex by reaction with PtCl2(NCPh)2. The related phosphinoxido-hexahydrophospinine oxide was taken in a similar sequence of reactions. Dibenzo[c.e][1,2]oxaphosphorines with a variety of P-substituents were also synthesized and used in complexations. In the first place, aryl-dibenzooxaphosporines were made available and than converted to the platinum complexes containing only one heterocyclic unit. Then a few P-alkoxy and P-amino dibenzooxaphosphorines including optically active derivatives were prepared and transformed to the corresponding platinum complexes that, in this particular case, contained two heterocyclic P-ligands in positioncis. Ring opening reaction accompanying the substitution of the starting chlorodibenzooxaphosphorine furnished a new P-ligand, 1-hydroxy-1 -diphenylphosphinobiphenyl that on reaction with the platinum precursor gave a bis(triarylphosphino) complex. The hydroxy-diphenylphosphino-biphenyl was modified by phosphorylation to furnish a special bidentate P-ligand and subsequently a ring Pt-complex. Aiming at the synthesis of further bidentate P-ligands, methylaminoethanol and L-ephedrine were reacted with two equivalents of chloro-dibenzooxaphosphorine. The resulting bis(dibenzooxaphosphorines) were utilized in the preparation of 7-ring platinum complexes.

AB - 2,4,6-Trialkylphenyl-1H-phospholes of certain extent of aromaticity displayed a special reactivity towards dichlorodibenzonitrileplatinum and gave a mixture of a monophosphole complex and a trans bis(phosphole) complex on reaction with the complexant. The 1H-phosphole 2H-phosphole sigmatropic rearrangement was utilised in the preparation of new P-ligands. A variety of 2,5-dihydro-1H-phosphole oxides were converted to 3-phosphabicyclo[3.1.0]hexane 3-oxides, 1,2-dihydrophosphinine oxides and 4-dichloromethylene-1,4-dihydrophosphinine oxides that after deoxygenation with silanes served as P-ligands in rhodium and palladium complexes. New phosphinine derivatives with exocyclic P-functions were developed by the Michael-addition of diphenylphosphine oxide to 1-phenyl-1,2-dihydrophosphinine oxide and by the double deoxygenation of the 1,2,3,6-tetrahydrophosphinine oxide so obtained. The bis(phosphine) was converted to a cis chelate complex by reaction with PtCl2(NCPh)2. The related phosphinoxido-hexahydrophospinine oxide was taken in a similar sequence of reactions. Dibenzo[c.e][1,2]oxaphosphorines with a variety of P-substituents were also synthesized and used in complexations. In the first place, aryl-dibenzooxaphosporines were made available and than converted to the platinum complexes containing only one heterocyclic unit. Then a few P-alkoxy and P-amino dibenzooxaphosphorines including optically active derivatives were prepared and transformed to the corresponding platinum complexes that, in this particular case, contained two heterocyclic P-ligands in positioncis. Ring opening reaction accompanying the substitution of the starting chlorodibenzooxaphosphorine furnished a new P-ligand, 1-hydroxy-1 -diphenylphosphinobiphenyl that on reaction with the platinum precursor gave a bis(triarylphosphino) complex. The hydroxy-diphenylphosphino-biphenyl was modified by phosphorylation to furnish a special bidentate P-ligand and subsequently a ring Pt-complex. Aiming at the synthesis of further bidentate P-ligands, methylaminoethanol and L-ephedrine were reacted with two equivalents of chloro-dibenzooxaphosphorine. The resulting bis(dibenzooxaphosphorines) were utilized in the preparation of 7-ring platinum complexes.

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