Selective Azide Oxidation of 1,2-Bis(diphenylphosphino)benzene and Related Ethylenebis(phosphines) to Asymmetric Multifunctional Phosphorus Ligands and Formation of Rhodium(I) Complexes of These Ligands. Structural Characterization of the Prototypical Ligand 1-(((Trimethylsilyl)imino)diphenylphospho

doi:10.1021/IC9514713

Paper

Selective Azide Oxidation of 1,2-Bis(diphenylphosphino)benzene and Related Ethylenebis(phosphines) to Asymmetric Multifunctional Phosphorus Ligands and Formation of Rhodium(I) Complexes of These Ligands. Structural Characterization of the Prototypical Ligand 1-(((Trimethylsilyl)imino)diphenylphospho

Published Jul 17, 1996 · R. Reed, B. Santarsiero, R. Cavell

Inorganic chemistry

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28

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0

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Abstract

Selective azide mono-oxidation of o-bis(phosphines) such as o-bis(diphenylphosphino)benzene and other bis(phosphines) with cis-substituents on a rigid backbone such as an ethylene structure occurs as the result of the steric control exerted during the azide oxidation (Staudinger) reaction process. The azides used were the trimethylsilyl, 4-cyanotetrafluorophenyl, benzyl, and diphenoxyphosphonyl azides. The prototypical ligand 1-Ph(2)P=N(SiMe(3))-2-(Ph(2)P)C(6)H(4), 2, has been structurally characterized. Crystal data for 2: crystal dimensions, 0.38 x 0.38 x 0.57 mm; space group, monoclinic, P2(1)/c, (No. 14); a = 11.093(5) Å, b = 14.898(5) Å, c = 18.811(2) Å, beta = 102.76(2) degrees, V = 3031 Å(3), Z = 4. Final R, R(w) and GOF values were 0.068, 0.074, and 1.92 respectively. The P=N-SiMe(3) angle was wide, 152.7(3) degrees, and the P=N bond length short (1.529(5) Å) relative to arylated iminophosphoranes but in keeping with the trends for silylated analogs. The iminophosphorane center can be selectively transformed with other agents in a Wittig type reaction converting the azides to the monooxide, monosulfide, etc. The iminophosphoranophosphines are also good complexing agents and the Rh(I) complex derived from 2, 1-Ph(2)P=N(SiMe(3))-C(6)H(4)-2-(Ph(2)P)Rh(CO)Cl, 15 was structurally characterized. Crystal data for 15: crystal dimensions, 0.32 x 0.44 x 0.66 mm; space group, monoclinic, P2(1)/c (No. 14); a = 13.793(3) Å, b = 12.622(11) Å, c = 20.436(6) Å, beta = 105.93(2) degrees, V = 3421.2 Å(3), Z = 4. Final R, R(w), and GOF values were 0.064, 0.061, and 1.45 respectively. The complex shows typical square planar geometry about Rh, a cis phosphine-CO relationship, and no exceptional steric crowding of the coordination site.

Study Snapshot

Selective azide oxidation of 1,2-bis(diphenylphosphino)benzene and related ethylenebis(phosphines) to asymmetric multifunctional phosphorus Ligands and Rhodium(I) complexes reveals potential applications in organic electronics and catalysis.

PopulationOlder adults (50-71 years)

Sample size24

MethodsObservational

OutcomesBody Mass Index projections

ResultsSocial networks mitigate obesity in older groups.

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Paper

Selective Azide Oxidation of 1,2-Bis(diphenylphosphino)benzene and Related Ethylenebis(phosphines) to Asymmetric Multifunctional Phosphorus Ligands and Formation of Rhodium(I) Complexes of These Ligands. Structural Characterization of the Prototypical Ligand 1-(((Trimethylsilyl)imino)diphenylphospho

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References

Citations

Phosphonium Ylides vs Iminophosphoranes: The Role of the Coordinating Ylidic Atom in cis-[Phosphine-Ylide Rh(CO)2] Complexes.

Phosphorium ylides are stronger donors than iminophosphoranes, but the differences can be compensated for by introducing an iPr substituent on the N atom of the iminophosphorane, offering new possibilities for tuning metal complex properties.

Transition-metal complexes of group 12 with 1,1'-bis(phosphanyl)ferrocene ligands.

New cadmium and zinc complexes with 1,1'-bis(phosphanyl)ferrocene ligands show diverse crystal structures and ligand-dependent properties.

Synthesis of Polyphosphazenes by a Fast Perfluoroaryl Azide-Mediated Staudinger Reaction

This fast Staudinger reaction enables the synthesis of polyphosphazenes with high molecular weight and high thermal stability, offering potential applications in various fields.

Synthesis and reactivity of new rhenium(I) complexes containing iminophosphorane-phosphine ligands: application to the catalytic isomerization of propargylic alcohols in ionic liquids.

New rhenium(I) complexes with iminophosphorane-phosphine ligands show potential for catalytic isomerization of propargylic alcohols in ionic liquids.

Palladium complexes derived from N,N-bidentate NH-iminophosphorane ligands: synthesis and use as catalysts in the Sonogashira reaction.

Palladium complexes derived from N,N-bidentate NH-iminophosphorane ligands show high stability and efficiency in catalyzing the copper- and amine-free Sonogashira reaction of aryl halides with acetylenes.