Synthesis of Symmetrical Bis-(2-chloro-1,3,2-benzodiazaphosphorinones) Hydrolysis and Fluorination of Selected Compounds

Fei, Zhaofu; Thönnessen, Holger; Jones, Peter G.; Schmutzler, Reinhard

doi:10.1002/(sici)1521-3749(199910)625:10<1732::aid-zaac1732>3.0.co;2-o

Cited by 8 publications

(1 citation statement)

References 10 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…The different isomers of 2F possess P–F distances from 1.519(6) to 1.594(2) Å. In related F–P(NR 2 ) 2 compounds, they are usually longer than 1.6 Å − with only one exception of d (P–F) = 1.588(2) Å while the sum of the covalent radii for a polarized P–F single bond even amounts to 1.66 Å . The averaged distance between the phosphorus atoms and the imine nitrogen atoms ( d Ø (P–N imine ) = 2.86(4) Å) lies significantly below the sum of their van der Waals radii (Σ r vdW (N···P) = 3.35 Å) .…”

Section: Resultsmentioning

confidence: 99%

On the Dynamic Behavior of Pacman Phosphanes─A Case of Cooperativity and Redox Isomerism

et al. 2023

View full text Add to dashboard Cite

In solution, the Pacman chlorophosphane (2Cl) shows fast exchange of the endo/exo-orientation of the two P−Cl bonds in the molecule featuring cooperativity. Experimental and quantum mechanical investigations of the inversion on the phosphorus(III) centers reveal a crucial role of chloride ions in the dynamic process. To confirm the results, the homologous Pacman halogen-phosphanes 2X were prepared by halogen exchange reactions (X = F, Br, and I). Besides accelerated dynamic behavior for the heavier analogues, significant differences in the molecular structure are caused by the halogen exchange reactions, including the formation of an endo−endo substituted Pacman fluorophosphane as well as dicationic species by phosphorus halogen bond dissociation. The latter process can be regarded as redox isomerism since two P III atoms in 2X become P V centers in the dications.

show abstract

Section: Resultsmentioning

confidence: 99%

On the Dynamic Behavior of Pacman Phosphanes─A Case of Cooperativity and Redox Isomerism

et al. 2023

View full text Add to dashboard Cite

show abstract

ChemInform Abstract: Synthesis of Symmetrical Bis‐(2‐chloro‐1,3,2‐benzodiazaphosphorinones). Hydrolysis and Fluorination of Selected Compounds.

et al. 1999

View full text Add to dashboard Cite

show abstract

Synthesis of Ethylene‐bridged Heterocyclic Bidentate P(III)N‐Ligands — Oxidation and Complexation Studies

Freytag

Jones

et al. 2003

Zeitschrift anorg allge chemie

View full text Add to dashboard Cite

A series of phosphor(III)inanone ligands 4-7, linked by ethylene bridges between the nitrogen atoms of the heterocyclic rings, were synthesized by the reaction of the bis-PCl derivative 3 with the appropriate trimethylsilylamines. The bis-phosphor(V)inanone compounds 8-11 were obtained by the oxidation of 4-7 with hexafluoroacetone (HFA). Oxidation of 4 and 6 with tetrachloroorthobenzoquinone (TOB) gave the bis-phosphor(V)inanones 12 and 13. The reaction of 4-6 with [Pt(COD)Cl 2 ] led to the platinum complexes 14-16. All the σ 3 -phosphorinanone compounds 4-7 and the σ 5 -phosphorinanone compounds 8-10, 12 and 13 exist as a mixture of two conformers, as indicated by two signals in the 31 P-NMR Synthese von ethylen-verbrückten heterocyclischen P(III)N-Liganden ؊ Untersuchungen der Oxidation und KomplexierungInhaltsübersicht. Eine Serie von Phosphor(III)-inanon-Liganden 4-7, durch Ethylengruppen zwischen den Stickstoffatomen der heterocyclischen Ringe verknüpft, wurden durch Umsetzung der Bis-PCl-Verbindung 3 mit den entsprechenden Trimethylsilylaminen synthetisiert. Die Bis-phosphor(V)-inanon-Verbindungen 8-11 wurden durch Oxidation von 4-7 mit Hexafluoraceton (HFA) erhalten. Die Oxidation von 4 und 6 mit Tetrachlor-o-benzochinon (TOB) führte zu den Bis-phosphor(V)-inanonen 12 und 13. Durch Umsetzung von 4-6 mit [Pt(COD)Cl 2 ] (COD ϭ 1,5-Cyclooctadien) wurden die Platinkomplexe 14-16 erhalten. Die σ 3 -Phosphorina-1953 spectra. However, compounds 9 and 11 exist as single conformers, both display only one sharp singlet in the 31 P-NMR spectra. The Pt-complexes 15 and 16 contain two conformers; one conformer of 16 could be isolated by crystallization. X-ray crystal structure determinations for compounds 8, 14 and 16 were conducted, revealing inversion symmetry for 8 and cis arrangement for 14 and 16.

show abstract

Synthesis of Symmetrical Bis-(2-chloro-1,3,2-benzodiazaphosphorinones) Hydrolysis and Fluorination of Selected Compounds

Abstract: The series of symmetrical bis-amides 3 was formed by the reaction of N-methylisatoic anhydride (1)

Cited by 8 publications

References 10 publications

On the Dynamic Behavior of Pacman Phosphanes─A Case of Cooperativity and Redox Isomerism

On the Dynamic Behavior of Pacman Phosphanes─A Case of Cooperativity and Redox Isomerism

ChemInform Abstract: Synthesis of Symmetrical Bis‐(2‐chloro‐1,3,2‐benzodiazaphosphorinones). Hydrolysis and Fluorination of Selected Compounds.

Synthesis of Ethylene‐bridged Heterocyclic Bidentate P(III)N‐Ligands — Oxidation and Complexation Studies

Contact Info

Product

Resources

About