Zeitschrift für anorganische und allgemeine Chemie

Volume 628, Issue 3 pp. 533-544

Article

Platinum(II) Complexes of P-Chiral 1, 8-Bis(diorganophosphino)naphthalenes; Crystal Structures of dmfppn, rac-[PtCl₂(dmfppn)], and rac-[PtCl₂(dtbppn)] (dmfppn = 1, 8-di(methyl-pentafluorophenylphosphino)naphthalene and dtbppn = 1, 8-di(tert-butylphenylphosphino)naphthalene)

Atilla Karaçar,

Atilla Karaçar

Braunschweig, Institut für Anorganische und Analytische Chemie der Technischen Universität

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Matthias Freytag,

Matthias Freytag

Braunschweig, Institut für Anorganische und Analytische Chemie der Technischen Universität

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Peter G. Jones,

Peter G. Jones

Braunschweig, Institut für Anorganische und Analytische Chemie der Technischen Universität

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Rainer Bartsch,

Rainer Bartsch

Braunschweig, Institut für Anorganische und Analytische Chemie der Technischen Universität

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Reinhard Schmutzler Prof. Dr.,

Corresponding Author

Reinhard Schmutzler Prof. Dr.

[email protected]

Braunschweig, Institut für Anorganische und Analytische Chemie der Technischen Universität

Institut für Anorganische und Analytische Chemie der Technischen Universität, Postfach 3329, D-38023 BraunschweigSearch for more papers by this author

Atilla Karaçar,

Atilla Karaçar

Braunschweig, Institut für Anorganische und Analytische Chemie der Technischen Universität

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Matthias Freytag,

Matthias Freytag

Braunschweig, Institut für Anorganische und Analytische Chemie der Technischen Universität

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Peter G. Jones,

Peter G. Jones

Braunschweig, Institut für Anorganische und Analytische Chemie der Technischen Universität

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Rainer Bartsch,

Rainer Bartsch

Braunschweig, Institut für Anorganische und Analytische Chemie der Technischen Universität

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Reinhard Schmutzler Prof. Dr.,

Corresponding Author

Reinhard Schmutzler Prof. Dr.

[email protected]

Braunschweig, Institut für Anorganische und Analytische Chemie der Technischen Universität

Institut für Anorganische und Analytische Chemie der Technischen Universität, Postfach 3329, D-38023 BraunschweigSearch for more papers by this author

First published: 18 March 2002

https://doi.org/10.1002/1521-3749(200203)628:3<533::AID-ZAAC533>3.0.CO;2-8

Citations: 26

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Abstract

The reaction of 1, 8-dilithionaphthalene 2, with 2 equivalents of rac-Me(C₆F₅)PCl, gave a 6 : 1 mixture of rac- and meso-1, 8-di(methyl-pentafluorophenylphosphino)naphthalene (dmfppn, rac-3h and meso-3h), but no reaction was observed when the sterically crowded rac-tBu(C₆F₅)PCl was used. In ³¹P NMR experiments, rac-3h and mmeso-3h exhibited characteristic signals (virtual quintets), which indicate that there is significant coupling through space (³J_PF + ⁷ J_PF ≈ 15 Hz). Compound rac-3h was isolated by fractional crystallisation and treated with aqueous H₂O₂ to yield the corresponding bis-phosphine dioxide, rac-7h. In contrast to rac-3h, there was no sign of through-space coupling in rac-7h, which again illustrates that the latter operates via the lone pairs at phosphorus.

Platinum(II) complexes were prepared from the new, P-chiral chelate rac-3h, and the related ligand 1, 8-di(tert-butylphenylphosphino) naphthalene (rac-dtbppn, rac-3e). All isolated new compounds were characterised by multinuclear NMR and IR spectroscopy, mass spectrometry, and elemental analysis. Single-crystal X-ray structure determinations were performed for rac-dmfppn (rac-3h), rac-[PtCl₂(dtbppn)] (rac-17e), and rac-[PtCl₂(dmfppn)] (rac-17h). rac-3h displays crystallographic twofold symmetry. In rac-17h, the electron-withdrawing effect of the C₆F₅ groups causes a shortening of the P_t—P bond to ca. 220 pm (cf. 223 pm in rac-17e).

Abstract

Platin(II)-Komplexe von P-chiralen 1, 8-Bis(diorganophosphino)naphthalinen; Röntgenstrukturanalysen von dmfppn, rac-[PtCl₂(dmfppn)] und rac-[PtCl₂(dtbppn)] (dmfppn = 1, 8-Di(methyl-pentafluorphenylphosphino)naphthalin und dtbppn = 1, 8-Di(tert-butylphenylphosphino)naphthalin)

Die Reaktion von 1, 8-Dilithionaphthalin (2) mit 2 Äquivalenten rac-Me(C₆F₅)PCl ergab ein 6 : 1 Gemisch von rac-und meso-1, 8-Di(methyl-pentafluorphenylphosphino)naphthalin (dmfppn, rac-3h und meso-3h). Wurde jedoch das sterisch anspruchsvollere rac-tBu(C₆F₅)PCl verwendet, konnte keine Reaktion beobachtet werden. In den ³¹P NMR Spektren zeigten rac-3h und meso-3h) charakteristische Signale (virtuelle Quintetts), die auf eine signifikante Kopplung durch den Raum deuten (³J_PF + ⁷ J_PF ≈ 15 Hz). Die Verbindung rac-3h wurde durch fraktionierende Kristallisation isoliert und ein Teil davon mit wässr. H₂O₂-Lösung versetzt, wodurch das entsprechende Bis-phosphinoxid (rac-7h) erhalten wurde. Anders als rac-3h, zeigte rac-7h keine Anzeichen für Kopplungen durch den Raum (through-space coupling), was erneut illustriert, daß diese Kopplungen durch die nicht-bindenden Elektronenpaare am Phosphor vermittelt werden.

Von dem neuen, P-chiralen Chelat-Liganden rac-3h und dem strukturell verwandten Liganden 1, 8-Di(tert-butylphenylphosphino)-naphthalin (rac-dtbppn, rac-3e) wurden Platin(II)-Komplexe hergestellt. Alle neuen Produkte wurden durch NMR und IR Spektroskopie, Massenspektrometrie und Elementaranalysen charakterisiert. Von den Verbindungen rac-dmfppn (rac-3h), rac-[ PtCl₂(dtbppn)] (rac-17e) und rac-[PtCl₂(dmfppn)] (rac-17h) wurden Einkristall-Röntgenstrukturanalysen angefertigt. rac-3h zeigt kristallographische, zweizählige Symmetrie. In rac-17h führt der elektronenziehende Effekt der C₆F₅-Gruppen zu einer Verkürzung der Pt—P Bindung auf ca. 220 pm (vgl. 223 pm in rac-17e).

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Volume628, Issue3

March 2002

Pages 533-544

Platinum(II) Complexes of P-Chiral 1, 8-Bis(diorganophosphino)naphthalenes; Crystal Structures of dmfppn, rac-[PtCl₂(dmfppn)], and rac-[PtCl₂(dtbppn)] (dmfppn = 1, 8-di(methyl-pentafluorophenylphosphino)naphthalene and dtbppn = 1, 8-di(tert-butylphenylphosphino)naphthalene)

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Platinum(II) Complexes of P-Chiral 1, 8-Bis(diorganophosphino)naphthalenes; Crystal Structures of dmfppn, rac-[PtCl2(dmfppn)], and rac-[PtCl2(dtbppn)] (dmfppn = 1, 8-di(methyl-pentafluorophenylphosphino)naphthalene and dtbppn = 1, 8-di(tert-butylphenylphosphino)naphthalene)

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Platinum(II) Complexes of P-Chiral 1, 8-Bis(diorganophosphino)naphthalenes; Crystal Structures of dmfppn, rac-[PtCl₂(dmfppn)], and rac-[PtCl₂(dtbppn)] (dmfppn = 1, 8-di(methyl-pentafluorophenylphosphino)naphthalene and dtbppn = 1, 8-di(tert-butylphenylphosphino)naphthalene)