Alkaliphosphor-verbindungen und ihr reaktives verhalten LVII. Über den substituenteneinfluss der reaktion von biphosphinen R2PPR2 mit phenyllithium

doi:10.1016/S0022-328X(00)82756-4

Journal of Organometallic Chemistry

Volume 13, Issue 2, August 1968, Pages 283-289

https://doi.org/10.1016/S0022-328X(00)82756-4 Get rights and content

Abstract

After establishing the procedure of the analysis of C₆H₅Li in the presence of LiPR₂ by means of model mixtures the cleavage of biphosphines, R₂PPR₂, by C₆H₅Li yielding LiPR₂ and C₆H₅PR₂ were studied quantitatively. The reaction rates decrease on changing from aryl to alkyl substituents as well as on lengthening of the alkyl chain in the series: C₆H₅ > CH₃ > C₂H₅ > n-C₃H₇ > n-C₄H₉ In the case of branched substituents, like isopropyl or tert-butyl groups, no reaction occurs.

Zusammenfassung

Es wird die Spaltung der Biphosphine R₂PR₂ durch C₆H₅Li, die zu LiPR₂ und C₆H₅PR₂ führt, quantitativ verfolgt, nachdem zuvor anhand von Modellmischungen die Bedingungen zur Ermittlung von LiC₆H₅ neben LiPR₂ festgelegt wurden. Die Umsetzungen verlangsamen sich bei Übergang von Aryl- zu Alkyl-substituenten sowie mit Verlängerung der Alkylkette entsprechend C₆H₅ > CH₃ > C₂H₅ > n-C₃H₇ > n-C₄H₉ und unterbleiben im Falle verzweigter Reste wie Isopropyl oder tert-Butyl.

Literatur (11)

K. Issleib und H. Weichmann, Chem. Ber., im...
K. Issleib et al.
Z. Anorg. Allg. Chem.
(1964)
K. Ziegler et al.
Justus Liebigs Ann. Chem.
(1930)
G. Wittig et al.
Ber.
(1944)
K. Issleib
Pure Appl. Chem.
(1964)

There are more references available in the full text version of this article.

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The reactions of R₂P–P(SiMe₃)₂ (R = Ph, ⁱPr and ⁱPr₂N) with BuLi in THF or DME solution lead to ion-contacted lithium derivatives R₂P–P(SiMe₃)Li · 3THF (R = ⁱPr, ⁱPr₂N) with tetrahedrally surrounded Li atoms and to the solvent-separated ionic [Li · 3DME]⁺[Ph₂P–PSiMe₃]⁻ with an octahedrally surrounded Li atom as confirmed by X-ray crystal structure analysis. The reaction of BuLi with Ph₂P–P(SiMe₃)₂ is accompanied with a significant side-reaction leading to Ph₂P–PPh₂ and to LiP(SiMe₃)₂.
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1998, Inorganica Chimica Acta
The reaction of yttrium tris [bis(trimethylilyl)methanide] (4) with bis (trimethylsilyl)phosphane in aromatic hydrocarbons yields dimeric yttrium tris [bis(trimethylsilyl)phosphanide] (5). The structure is deducted from NMR data. The quadruply coordinated phosphorus nuclei of the two bridging ligands show a triplet of quintets due to the coupling with both the yttrium and the four terminal bound phosphorus atoms, whereas the ³¹P(¹H) resonance of the terminal phosphanide ligands split to doublets of triplets. The $^{1} J(^{89} Y,^{31} P)$ coupling constants for the triply coordinated terminal phosphorus atoms are 122.4 Hz; for the μ-coordinated phosphorus atom a much smaller value of 56.7 Hz is observed. A synthesis of a yttrium tris(phosphanide) via the metathesis reaction of lithium di-tert-butylphosphanide and yttrium(III)chloride failed, only [(thf)₂LiCl]₂ (1) as well as [(thf)LiCl·(thf)₂Li¹PBu₂]₂ (2) were crystallized from a tetrahydrofuran solution. Crystallographic data for 2: monoclinic, $P2_{1} /n, a=963.3(2), b=1486.1(3), c=1760.7(4) pm, β=92.51(3)°, Z=2 dimers, wR_{2} =0.1452; for 4$ : hexagonal, P31c, a=b=1629.50(9), c=860.14(7), Z=2, wR₂=0.1854.
Die heterogen katalysierte Co-oligomerisation von 1,3-Butadien und CO<inf>2</inf> mit immobilisierten Palladiumkomplexen
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Immobilized catalysts prepared from [Pd(η⁵-C₅H₅)(η³-C₃H₅)] (5) and polymer bound phosphines 4a–c are used to catalyse C,C coupling reactions of carbon dioxide and any organic co-substrate for the first time in a heterogeneous way. These phosphines, synthesised from chloromethylated polystyrene, are characterised by their elemental analysis data and NMR spectra. The immobilized catalyst from polymer 4a and 5 catalyses the formation of the δ-lactone 2-ethylidene-6-heptene-5-olid (1). With low reaction rates, up to 72% selectivity to 1 is observed, These catalysts can be used in multiple reactions. In an analogous procedure using polymer 4b, the synthesis of C₁₇ carboxylic esters is successful.
Mit immobilisierten Katalysatoren aus polymergebundenen Phosphinen und [Pd(η⁵-C₅H₅)(η³-C₃H₅)] (5) werden erstmals heterogen katalytische C,C-Verknüpfungsreaktionen zwischen Kohlendioxid und einem organischen Cosubstrat ermöglicht. Die in dieser Arbeit eingesetzten Phosphine werden ausgehend von chlormethyliertem Polystyrol synthetisiert und durch ihre elementaranalytischen Zusammensetzungen und ihre NMR-Spektren charakterisiert. Immobilisierte Katalysatoren aus Polymer 4a und 5 katalysieren die Bildung des δ-Lactons 2-Etyliden-hepten-5-olid (1). Bei geringen Reaktionsgeschwindigkeiten wird bis zu 72% Selektivität an 1 erzielt. Diese Katalysatoren lassen sich mehrfach wiederverwenden. Bei analoger Vorgehensweise gelingt durch den Einsatz des Polymers 4b die katalytische Synthese von C₁₇—Carbonsäureestern als Kopplungsprodukte.
The reactivity of organoelement compounds with aluminium-aluminium, gallium-gallium and indium-indium bonds
1997, Coordination Chemistry Reviews
Organoelement derivatives with aluminium—aluminium, gallium—gallium and indium—indium bonds were synthesized for the first time in our group eight years ago. They show a remarkable and unprecedented chemical reactivity and up to now six different types of reaction have been found, which are summarized in this review article: (i) The formation of adducts is observed with sterically less shielded Lewis-bases like H⁻ or Br⁻. (ii) The treatment with strong reducing agents like the alkali metals or some alkyllithium derivatives yields radical anions with le-M-M π bonds. (iii) Sterically more shielded bases give a deprotonation of the substituent with the formation of heterocycles. (iv) Insertion reactions into the element—element bonds could be realized with atoms, whole molecules or molecular fragments. (v) A metathesis reaction with a ditellurium derivative gives a monomeric organo gallium telluride. (vi) An exchange of two alkyl substituents with the preservation of the element—element bond is observed by the reaction with carboxylic acids.
Bis(diisopropylgalliumdiisopropylphosphid) und -arsenid. Kristallstruktur des phosphidderivats-ein "angedeuteter" butterfly
1992, Journal of Organometallic Chemistry
The smallest folding angle yet to be found of a four membered gallium-heteroatom ring system with butterfly geometry is in the title compound [iPr₂GaP(ⁱPr₂)]₂ (II). The synthesis of this compound and of its arsenide homologue (III) via the reaction of ⁱPr₃Ga with the H-acidic compounds ⁱPr₂EH (E  P, As) is reported. Both compounds react below the decomposition temperature of 400°C, splitting off propene and propane, respectively. They may be suitable organometallic precursors for III/V-layer compounds. On the other hand, the reaction of ⁱPr₃Ga with ^tBu₂AsH leads only to the formation of the corresponding Lewis acid-base adduct ⁱPr₃Ga·.As(H)^tBu₂ (IV). Spectra and some physical and chemical properties of the new compounds II–IV are reported.
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The synthesis of tridentate dialkylamino ligands containing tertiary phosphorus or arsenic donors
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Use of the trimethylsilyl protecting function on nitrogen enables the high yield preparation of the potentially tridentate ligands of the type HN(CH₂CH₂ ER₂)₂ (E = P; R = Me, Et, ⁱPr and E = As; R = Me, Et) by nucleophillic substitution of halide in Me₃SiN (CH₂CH₂Cl)₂. The di-isopropylphosphino and diethylarsino derivatives have not previously been reported, the other derivatives described are now available in considerably improved yields via this new route. The failure of syntheses or poor yields obtained from unprotected amine precursors is explained by aziridine formation. Deprotonation of the amines provides series of chelating dialkylamido ligands enabling access to new classes of novel complexes.

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^☆: Für LVI. Mitteilung siehe Ref. 1.

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Journal of Organometallic Chemistry

Abstract

Zusammenfassung

Literatur (11)

Z. Anorg. Allg. Chem.

Justus Liebigs Ann. Chem.

Ber.

Pure Appl. Chem.

Cited by (49)

Syntheses and crystal structures of lithium derivatives of diphosphanes R<inf>2</inf>P-P(SiMe<inf>3</inf>)Li · 3L, R = Ph, <sup>i</sup>Pr and <sup>i</sup>Pr<inf>2</inf>N, L = THF or DME

Syntheses and structure of dimeric yttrium tris [bis(trimethylsilyl)phosphanide]; X-ray structures of [(thf)LiCl · (thf)<inf>2</inf>LiP<sup>t</sup>Bu<inf>2</inf>]<inf>2</inf> and Y [CH(SiMe<inf>3</inf>)<inf>2</inf>]<inf>3</inf>

Die heterogen katalysierte Co-oligomerisation von 1,3-Butadien und CO<inf>2</inf> mit immobilisierten Palladiumkomplexen

The reactivity of organoelement compounds with aluminium-aluminium, gallium-gallium and indium-indium bonds

Bis(diisopropylgalliumdiisopropylphosphid) und -arsenid. Kristallstruktur des phosphidderivats-ein "angedeuteter" butterfly

The synthesis of tridentate dialkylamino ligands containing tertiary phosphorus or arsenic donors

Alkaliphosphor-verbindungen und ihr reaktives verhalten LVII. Über den substituenteneinfluss der reaktion von biphosphinen R2PPR2 mit phenyllithium☆

Abstract

Zusammenfassung

Z. Anorg. Allg. Chem.

Justus Liebigs Ann. Chem.

Ber.

Pure Appl. Chem.

Alkaliphosphor-verbindungen und ihr reaktives verhalten LVII. Über den substituenteneinfluss der reaktion von biphosphinen R₂PPR₂ mit phenyllithium☆