Polyfunctional ligands: comparative oxidative coupling of [E(PPh2)2]–(E = CH, N) with iodine

Braunstein, Pierre; Hasselbring, Reinhard; Tiripicchio, António; Ugozzoli, Franco

doi:10.1039/c39950000037

Cited by 38 publications

(46 citation statements)

References 24 publications

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“…In contrast, the oxidative coupling of 1 with iodine [9] leads to the PϪP coupled diphosphazene Ph 2 PϪNϭPPh 2 ϪPPh 2 ϭNϪPPh 2 (2), that can also be obtained by the reaction of 1 with anhydrous iron(3ϩ) fluoride, copper(2ϩ) fluoride [10] , bismuth tribromide or antimony triiodide [11] . On the other hand, a mixture of arsenic triiodide and 1 in the molar ratio of 1:2 reacts at 20°C to yield 2 and the As(1ϩ) complex D [11] .…”

mentioning

confidence: 99%

Synthesis and X-Ray Structures of Novel Lead(1+) and Indium(3+) Phosphazenide Complexes; Detailed207Pb-NMR Spectra of the207Pb-Labelled Dimeric Lead(1+) Species

Winkler¹,

Bauer²,

Heinemann³

et al. 1998

Eur. J. Inorg. Chem.

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The reaction of PbCl2 with LiN(PPh2)2 (1) at −78°C affords the P−P coupled phosphazene Ph2P−N=PPh2−PPh2=N−PPh2 (2) as an oxidation product and, as a reduction equivalent, the novel lead(1+) complex [(Pb1+)2(μ‐Ph2P···N···PPh2−)2](Pb−Pb) (3). The crystal structure determination of the red compound 3 shows a Pb−Pb bond length of 304.1(1) pm. The 31P‐ and 207Pb‐NMR spectra of 3 are complicated due to the presence of a higher order spin system (AA′A′′A′′′X for the mono‐207Pb isotopomer, AA′A′′A′′′XX′ for the bis‐207Pb isotopomer). Simulations of the 31P and 207Pb spectra both on material with natural isotope abundance and on the 207Pb‐labelled compound (3*) reveal a large Pb,Pb coupling constant of 7708 Hz, indicative of a covalent Pb−Pb bond. − Though InCl3 is diagonally related to PbCl2, no significant redox process is observed in the reaction between InCl3 and 1. The yellow crystals of [In3+(Ph2P···N···PPh2−)3] (4) that are obtained were also investigated by X‐ray analysis. These show a propeller‐like configuration of the three four‐membered chelate rings with indium(3+) as the centre.

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confidence: 99%

Synthesis and X-Ray Structures of Novel Lead(1+) and Indium(3+) Phosphazenide Complexes; Detailed207Pb-NMR Spectra of the207Pb-Labelled Dimeric Lead(1+) Species

Winkler¹,

Bauer²,

Heinemann³

et al. 1998

Eur. J. Inorg. Chem.

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“…The product does not appear to be light-sensitive. Yield: 81% (0.061g) 31 (5). A solution of chlorodiphenylphosphine (2.306 g, 10.05 mmol) in toluene (ca.…”

Section: Inorganic Chemistrymentioning

confidence: 99%

“…99% (4.800 g, 10.2 mmol). 31 (20 mL) was added a solution of 5 (1.391 g, 2.95 mmol) in THF (30 mL) at −78°C. The reaction mixture was stirred for 2 h before the resulting KBr was removed by filtration.…”

Section: Inorganic Chemistrymentioning

confidence: 99%

Low-Valent Chemistry: An Alternative Approach to Phosphorus-Containing Oligomers

et al. 2014

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A convenient preparative approach to low-valent phosphorus-rich oligomers is presented. Ligand substitution reactions involving anionic diphosphine ligands of the form [(PR2)2N](-) and [(PPh2)2C5H3](-) and a triphosphenium bromide P(I) precursor result in the formation of phosphorus(I)-containing heterocycles, several of which are of types that have never been prepared before. The methodology described also allows for the preparation of the known heterocycle cyclo-[P(PPh2)N(PPh2)]2 in better yields and purity than the synthetic approach reported previously. Preliminary reactivity studies demonstrate the viability of such zwitterionic oligomers as multidentate ligands for transition metals.

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“…1) und des Toluols kristallisiert aus der ®ltrierten Lo Èsung auf Zugabe von n-Pentan das Rubidium-bis(diphenylphosphanyl)amid (6a) in feinen, hellgelben Nadeln aus. Sie sind aufgrund HNPPh 2 (5) 307.4 (5) Cs (1)±O (2) 307.8(6) Cs(1)±O (4) 307.6(4) Cs(1)±O (3) 310.3 (7) Cs (1)±O(1) 311.9 (7) Cs (1)±O (6) 319.4(5) Cs(1)±C (20) 342.9 (6) Cs (1)±C (21) 347.9(7) Cs(1)±N (1) 351.4(4) P(1)±N (1) 163.2(4) P(1)±C (30) 182.2(6) P(1)±C (20) 184.2(6) P(2)±N (1) 165 (1) 99.0(2) P(2)±N(1)±Cs(1) 144.9(2) P(1)±C (20) (10) 316.4 (6) Cs (2)±O (8) 317.4(6) Cs(2)±O (12) 318.4 (7) Cs(2)±O (7) 330.7(6) Cs(2)±O (9) 340.4 (6) Cs (2)±O (11) 342.0(6) P(1)±N (1) 154.0(6) P(1)±C (11) 186.2(8) P(2)±N (2) 152.9(6) P (2) Da in dem Anion [N(PPh 2 ) 2 ] À von 6a,b±8 die beiden Phosphoratome miteinander koppeln ( 2 J PP ), geben die 13 C-Spektren Anlaû zu Multipletts, die nicht nach den Regeln erster Ordnung interpretiert werden ko Ènnen [43]. Man beobachtet in den 13 Es zeigt sich, daû sowohl P(1) als auch P(2) nahezu axialsymmetrische Verschiebungstensoren mit sehr kleinen Asymmetrieparametern aufweisen ( P1 0.049; P2 0.017).…”

Section: Pra èParative Ergebnisse Und Reaktionenunclassified

Chemie polyfunktioneller Molekäle, 130. Mitt. [1]: Rubidium- und Cäsium-bis(diphenylphosphanyl)amid – Synthesen, (18-Krone-6)-Komplexe, Spaltprodukte, Kristallstrukturen und Festkörper-NMR-Spektren

Ellermann

Bauer

Schütz

et al. 1998

Monatshefte fuer Chemie

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The metalation of bis(diphenylphosphanyl)amine, HN(PPh 2 ) 2 (5), with RbOtBu in the presence of N,N,N H ,N HH ,N HH -pentamethyldiethylenetriamine (PMDTA (3)) in toluene surprisingly affords the nearly PMDTA free RbN(PPh 2 ) 2 (6a). Recrystallization of 6a from tetrahydrofuran (THF) yields RbN(PPh 2 ) 2 Á 0.5 THF (6b). Compounds 6a, b crystallize in thin needles; however, these are not suitable for X-ray structure analyses. The reactions of 5 with MOtBu (M Rb, Cs) in the presence of 18-crown-6 in toluene yield the monomeric, pale yellow rubidium and caesium complexes [Rb(18-crown-6)(N(PPh 2 ) 2 )] (7) and [Cs(18-crown-6)(N(PPh 2 ) 2 )] (8), respectively. Allowing to stand a solution of 8 in THF for three months at 20 C results in a cleavage product of 8. This is identi®ed as the dimeric yellow complex [(Cs(18-crown-6)) 2 ("-N=P(H)Ph 2 ) 2 ] Á THF (9). The source of the hydrogen atom in the bridging phosphorane iminate anion [ a a n n N=P(H)Ph 2 ] À is uncertain. Compounds 7±9 are structurally characterized by X-ray analyses. These reveal that [N(PPh 2 ) 2 ] À acts as P-ligating chelate in 7, whereas it coordinates the Cs as N-donor as well as 2 C-donor with one phenyl group in 8. No phosphorus coordination is observed in 8. The two caesium cations in 9 are two-fold N-bridged by [ a a n n N=P(H)Ph 2 ] À . The coordination sphere of each caesium atom is completed by a 18-crown-6 ligand. The solid state 13 C NMR spectrum of 8 reveals dynamic phenomena (rotation of the 18-crown-6 ligand). In the solid state 31 P spectrum of 8, 31 P, 31 P±J-coupling is observed between the chemically non-equivalent phosphorus sites (J 390 Hz).

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Polyfunctional ligands: comparative oxidative coupling of [E(PPh₂)₂]^–(E = CH, N) with iodine

Cited by 38 publications

References 24 publications

Synthesis and X-Ray Structures of Novel Lead(1+) and Indium(3+) Phosphazenide Complexes; Detailed207Pb-NMR Spectra of the207Pb-Labelled Dimeric Lead(1+) Species

Synthesis and X-Ray Structures of Novel Lead(1+) and Indium(3+) Phosphazenide Complexes; Detailed207Pb-NMR Spectra of the207Pb-Labelled Dimeric Lead(1+) Species

Low-Valent Chemistry: An Alternative Approach to Phosphorus-Containing Oligomers

Chemie polyfunktioneller Molekäle, 130. Mitt. [1]: Rubidium- und Cäsium-bis(diphenylphosphanyl)amid – Synthesen, (18-Krone-6)-Komplexe, Spaltprodukte, Kristallstrukturen und Festkörper-NMR-Spektren

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