ISSN:
0009-2940
Keywords:
Arsenic, two-coordinate
;
Phoshorus, two-coordinate
;
Phosphinines
;
Phosphabenzenes
;
Arsadiphosphabenzenes
;
Chemistry
;
Inorganic Chemistry
Source:
Wiley InterScience Backfile Collection 1832-2000
Topics:
Chemistry and Pharmacology
Notes:
1,1-Bis[(diphenylphosphanyl)methyl]ethene (3) reacts with PCl3 or AsCl3 in the presence of SnCl2 as a reducing agent to form cationic heterocycles in which the two newly generated phosphonium centers are bridged by two-coordinate, negatively charged phosphorus (4a) or arsenic (4b) centers. Hexachlorostannate(IV) dianions function as counterions to these heterocycles, in which the exocyclic methylene group is retained. By treatment of 4a with a base a rearrangement is induced which includes a proton migration from an endo-to the exocyclic CH2 group to give 5-methyl-1,1,3,3-tetraphenyl-1λ5,2λ3,3λ51-triphosphinine (5), a novel 1,2,3-triphosphabenzene species. The reaction of the arsenic compound 4b with base did not yield the corresponding arsa-diphosphabenzene, but gave only decomposition products. Compound 4b · 0.5 CH3CN has been studied by X-ray crystallography. The six-membered heterocycle shows a chair conformation with an arsenic atom solely coordinated by two phosphorus atoms at roughly equal distances with a sharp angle P - As - P of only 93.0(1)°.
Additional Material:
1 Ill.
Type of Medium:
Electronic Resource
URL:
http://dx.doi.org/10.1002/cber.19931260309
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