ISSN:
0044-2313
Keywords:
Spirocyclic metallaphosphazene complexes of nickel and palladium
;
preparation
;
IR, Raman, NMR, UV/VIS, mass spectra
;
crystal structures
;
Chemistry
;
Inorganic Chemistry
Source:
Wiley InterScience Backfile Collection 1832-2000
Topics:
Chemistry and Pharmacology
Description / Table of Contents:
Chemistry of Polyfunctional Molecules. 111. Synthesis and Structure of Novel Spirocyclic Nickel(II) and Palladium(II) Complexes with the Phosphazene Anion [Ph2P\documentclass{article}\pagestyle{empty}\begin{document}$ \underline {.\,.} $\end{document}N\documentclass{article}\pagestyle{empty}\begin{document}$ \underline {.\,.} $\end{document}P(Ph)2\documentclass{article}\pagestyle{empty}\begin{document}$ \underline {.\,.} $\end{document}N\documentclass{article}\pagestyle{empty}\begin{document}$ \underline {.\,.} $\end{document}PPh2]-When anhydrous MCl2 (M = Ni, Pd) is treated with LiN(PPh2)2 (1) in the molar ratio 1:2 in boiling toluene for 60 hours the new spirocyclic metallaphosphazenes (4a, b; M = Ni, Pd) are obtained by oxidative scrambling of the P—N—P anion in 1. N(PPh2)3 (3), the elemental metals and LiCl are also formed. The compounds 4a, b are characterized by IR, Raman, 31P{1H}NMR, 1H-NMR, 13C{1H} NMR, and FD mass spectra. The X-ray crystal structures of 4a X 1 CH2Cl2 and 4b X 0,597 CH2Cl2 show that the metals in 4a, b occupy a mid-position between tetrahedral and square planar coordination. Both rings in 4a, b show a torsion angle of nearly 45° at the spirocyclic metal centre.
Notes:
Wasserfreies MCl2 (M = Ni, Pd) reagiert mit LiN(PPh2)2 (1) im Molverhältnis 1:2 in siedendem Toluol während 60 Stunden unter teilweiser Spaltung und Umgruppierung von 1 zu den neuen spirocyclischen Metallaphosphazenen (4a, b; M = Ni, Pd), N(PPh2)3 (3), elementarem Metall und LiCl. Die Verbindungen 4a, b werden durch IR-, Raman-, 31P{1H}-NMR-, 1H-NMR-, 13C{1H}-NMR- und FD-Massen-Spektren sowie durch Röntgenkristallstrukturanalysen charakterisiert. Letztere zeigen, daß die Metallkoordinationspolyeder in 4a, b eine Mittelstellung zwischen tetraedrischer und quadratisch-planarer Koordination einnehmen. Die beiden Ringe in 4a, b sind am Spirometallzentrum um etwa 45° gegeneinander verdrillt.
Additional Material:
3 Ill.
Type of Medium:
Electronic Resource
URL:
http://dx.doi.org/10.1002/zaac.19936191208
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