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Phosphaniminate von Alkalimetallen: Die Kristallstrukturen von [KNPCy 3 ] 4 , [KNPCy 3 ] 4 ·2OPCy 3 , [CsNPCy 3 ] 4 ·4OPCy 3 und [Li 4 (NPPh 3 )(OSiMe 2 NPPh 3 ) 3 (DME)]
Author(s) -
Gröb Thorsten,
Chitsaz Soheila,
Harms Klaus,
Dehnicke Kurt
Publication year - 2002
Publication title -
zeitschrift für anorganische und allgemeine chemie
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.354
H-Index - 66
eISSN - 1521-3749
pISSN - 0044-2313
DOI - 10.1002/1521-3749(200202)628:2<473::aid-zaac473>3.0.co;2-z
Subject(s) - chemistry , liquid ammonia , crystal structure , crystallography , amide , alkali metal , metal , lattice constant , stereochemistry , ammonia , organic chemistry , physics , diffraction , optics
The alkalimetal phosphoraneiminates [KNPCy 3 ] 4 , ( 1 ) [KNPCy 3 ] 4 ·2OPCy 3 ( 2 ) and [CsNPCy 3 ] 4 ·4OPCy 3 ( 3 ) (Cy = cyclohexyl ) which are obtainable by the reaction of pottassium amide or cesium amide with Cy 3 PI 2 or Cy 3 PBr 2 in liquid ammonia, as well as the lithium derivative [Li 4 (NPPh 3 )(OSiMe 2 NPPh 3 ) 3 (DME)] ( 4 ) have been characterized by crystal structure determinations. 4 has been formed by the insertion reaction of silicon greaze (‐OSiMe 2 )n into the LiN bonds of [LiNPPh 3 ] 6 in DME solution (DME = 1, 2‐dimethoxyethane). 1 : Space group P&1macr;, Z = 2, lattice dimensions at 193 K: a = 1389.8(1); b = 1408.1(1); c = 2205.2(2) pm; α = 78.952(10)?; β = 81.215(10)?; γ = 66.232(8)?; R1 = 0.0418. 2 : Space group Pbcn, Z = 4, lattice constants at 193 K: a = 2943.6(2); b = 2048.2(1); c = 1893.8(1) pm; R1 = 0.0428. 3 : Space group Cmc2 1 , Z = 4, lattice dimensions at 193 K: a = 2881.6(2); b = 2990.2(2); c = 1883.7(2) pm; R1 = 0.0586. 4 ·1/2DME: Space group R&3macr;c, Z = 12, lattice dimensions at 193 K: a = b = 1583.5(1); c = 11755.3(5) pm; R1 = 0.0495. All complexes have heterocubane structures. In 1‐3 they are formed by four alkali metal atoms and by the nitrogen atoms of the (μ 3 ‐NPCy 3 ‐ ) groups, whereas 4 forms a "heteroleptic" Li 4 NO 3 heterocubane.