In:
Zeitschrift für anorganische und allgemeine Chemie, Wiley, Vol. 629, No. 12-13 ( 2003-01), p. 2398-2407
Abstract:
Synthesis, Properties, and Molecular Structures of 2, 3, 4, 5‐Tetraethylphospholides of the Alkali Metals Sodium, Potassium, Rubidium, and Cesium as well as Metathesis Reactions of the Potassium Derivatives with Tin(II) Chloride and Gallium(III) Chloride The reduction of chloro‐2, 3, 4, 5‐tetraethylphosphole with sodium, potassium, rubidium, and cesium in THF or 1, 2‐dimethoxyethane (DME) yields nearly quantitatively after recrystallization from a DME solution the corresponding alkali metal 2, 3, 4, 5‐tetraethylphospholides (DME)Na(PC 4 Et 4 ) ( 1 ), K(PC 4 Et 4 ) ( 2 ), (DME)Rb(PC 4 Et 4 ) ( 3 ), and (DME)Cs(PC 4 Et 4 ) ( 4 ). If the chloro‐2, 3, 4, 5‐tetraethylphosphole still contains zirconocene dichloride from its preparation heteroleptic (THF)CsC 5 H 5 ·Cs(PC 4 Et 4 ) ( 5 ) precipitates. Whereas the sodium derivative 1 crystallizes as a dimer, the phospholides 2 to 4 of the heavier alkali metals crystallize as one‐dimensional polymers. Due to the size of the potassium cation no additional ether ligands are coordinated to this metal atom and a linear column precipitates, whereas for the Rb and Cs compounds the DME complexes are formed thus leading to a zig‐zag chain. The substitution of half of the phospholide anions by cyclopentadienide ligands in 5 leads to a three‐dimensional network in the crystalline state. The metathesis reaction of the potassium derivative 2 with GaCl 3 and SnCl 2 yields dimeric (DME)K[(μ‐Cl) 4 Ga 2 (PC 4 Et 4 ) 3 ] ( 6 ) and monomeric Sn(PC 4 Et 4 ) 2 ( 7 ), respectively. Whereas in the alkali metal phospholides 1 to 5 a high degree of delocalization of the anionic charge within the five‐membered ring and a η 5 ‐coordination are realized, the 2, 3, 4, 5‐tetraethylphospholide anion is σ‐bonded to gallium(III) in 6 and to tin(II) in 7 .
Type of Medium:
Online Resource
ISSN:
0044-2313
,
1521-3749
DOI:
10.1002/zaac.v629:12/13
DOI:
10.1002/zaac.200300264
Language:
English
Publisher:
Wiley
Publication Date:
2003
detail.hit.zdb_id:
201094-X
detail.hit.zdb_id:
1481139-X
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