Phosphoraneiminato complexes of zirconium: Crystal structures of [ZrCl₃(NPPh₃)(HNPPh₃)₂] and [ZrCl₂(NPPh₃)₂(HNPPh₃)₂]

Titelangaben

Gröb, Thorsten ; Geiseler, Gertraud ; Harms, Klaus ; Greiner, Andreas ; Dehnicke, Kurt:
Phosphoraneiminato complexes of zirconium: Crystal structures of [ZrCl₃(NPPh₃)(HNPPh₃)₂] and [ZrCl₂(NPPh₃)₂(HNPPh₃)₂].
In: Zeitschrift für anorganische und allgemeine Chemie. Bd. 628 (2002) Heft 1 . - S. 217-221.
ISSN 1521-3749
DOI: https://doi.org/10.1002/1521-3749(200201)628:1<217::AID-ZAAC217>3.0.CO;2-G

Volltext

Link zum Volltext (externe URL):

Abstract

The phosphoraneiminato complexes ZrCl3-(NPPh3)(HNPPh3)(2)] (1) and ZrCl2(NPPh3)(2)(HNPPh3)(2)] (2) have been obtained by reaction of ZrCl4(THF)(2)] with CsNPPh3](4) in THF solution to give colourless moisture sensitive crystals which are characterized by X-ray structure de-terminations. ZrCl3(NPPh3)(HNPPh3)(2)] (1): Space group P(1) over bar, Z = 2, lattice dimensions at 193 K: a = 1209.4(2); b = 1480.8(2), c =: 1814.2(2) pm; alpha = 71.203(13)degrees, beta = 71.216(13)degrees, gamma = 74.401(13)degrees; R = 0.0476. The zirconium atom of 1 is oktahedrally coordinated by the three chlorine atoms in meridional arrangement and by the three nitrogen atoms of the (NPPh3-) ligand and of the two phosphane imine molecules HNPPh3. The ZrN bond distance of the (NPPh3-) group (193.5 pm) corresponds with a double bond. ZrCl2(NPPh3)(2)(HNPPh3)(2)] (2): Space group P(1) over bar, Z = 4, lattice dimensions at 193 K: a = 1447.6(2); b = 1925.7(2), c = 2457.0(2) pm, alpha = 67.317(12)degrees, beta = 87.376(12)degrees, gamma = 87.103(13)degrees; R = 0.0408. The zirconium atom in 2 is octahedrally coordinated by the two chlorine atoms in trans position, and by the nitrogen atoms of the two (NPPh3-) groups as well as by the two HNPPh3 molecules. The ZrN distance of the (NPPh3-) ligands (198.9 and 202.0 pm) suggest some pi-interaction between the zirconium and the nitrogen atoms.