Chemie polyfunktioneller Moleküle. 111. Synthese und Struktur neuartiger spirocyclischer Nickel(II)‐ und Palladium(II)‐Komplexe mit dem Phosphazen‐Anion [Ph₂P\documentclass{article}\pagestyle{empty}\begin{document}$ \underline {.\,.} $\end{document}N\documentclass{article}\pagestyle{empty}\begin{document}$ \underline {.\,.} $\end{document}P(Ph₂)\documentclass{article}\pagestyle{empty}\begin{document}$ \underline {.\,.} $\end{document}N\documentclass{article}\pagestyle{empty}\begin{doc

Abstract

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.

Rearrangement of phosphinohydrazide ligand –NPh-N(PPh2)2 in transition metal coordination sphere: Synthesis and characterization of nickel and cobalt spirocyclic complexes M(NPh-PPh2N-PPh2)2 and their properties

“…The Co(1)-P(2,4) and Co(1)-N(1,3) distances in 2 are 2.3376(6), 2.3164(6) Å and 1.944(2), 1.987(2) Å , respectively. It is worth to cite an instance of related spirocyclic cobalt(II) phosphazene complex Co[Ph 2 PNPPh 2 -NPPh 2 ] 2 (5) [6,7], which can be considered as a N(1)-capped CoP 4 tetrahedron or as a distorted tetragonal pyramid with an apical P(3) and a N(1)-P(1)-P(4)-P(6) base. The complex is in low-spin electronic state showing l eff = 2.39 l B .…”

Reversal of polarization in amidophosphines: neutral- and anionic-κP coordination vs. anionic-κP,N coordination and the formation of nickelaazaphosphiranes

“…The conformations about the exocyclic P-N bonds are exo, i.e., the lone-pairs of electrons on the phosphorus atoms are pointing outward Fig. 6 Thermal ellipsoid (30%) plot and partial labeling scheme of 9a. All but the amino hydrogen atoms have been omitted, and the tert-butyl groups are drawn as sticks only.…”

“…The ambidentate amidophosphines have been shown to chelate metals through either nitrogen (jN), 4 phosphorus (jP) 5 or through both atoms simultaneously (jP,N). [6][7][8] Depending on one's inclination the bis(tert-butylamino)diazadiphosphetidine 1 (Chart 1) may be regarded as either a cyclic diphosphine or a cyclic tetraamine. 9 In the former role this heterocycle had garnered some attention as neutral phosphorus-donor ligand for transition metals.…”

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

“…140°C (dec.). 3 was mixed with 12 ml of a concentrated aqueous solution of HCl. After the initially brisk foaming up had ceased the clear colourless solution was stirred for 10 min at 20°C.…”