Phosphaniminate von Alkalimetallen: Die Kristallstrukturen von [KNPCy3]4, [KNPCy3]4·2OPCy3, [CsNPCy3]4·4OPCy3 und [Li4(NPPh3)(OSiMe2NPPh3)3(DME)] |
| |
Authors: | Thorsten Grb Soheila Chitsaz Klaus Harms Kurt Dehnicke |
| |
Abstract: | The alkalimetal phosphoraneiminates KNPCy3]4, ( 1 ) KNPCy3]4·2OPCy3 ( 2 ) and CsNPCy3]4·4OPCy3 ( 3 ) (Cy = cyclohexyl) which are obtainable by the reaction of pottassium amide or cesium amide with Cy3PI2 or Cy3PBr2 in liquid ammonia, as well as the lithium derivative Li4(NPPh3)(OSiMe2NPPh3)3(DME)] ( 4 ) have been characterized by crystal structure determinations. 4 has been formed by the insertion reaction of silicon greaze (‐OSiMe2)n into the LiN bonds of LiNPPh3]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 Cmc21, 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 (μ3‐NPCy3‐) groups, whereas 4 forms a "heteroleptic" Li4NO3 heterocubane. |
| |
Keywords: | Phosphoraneiminates Cesium Potassium Lithium Crystal structures |
|
|