Beiträge zur Chemie des Phosphors. 224. Zur Thermolyse von 1,2-Di-tert-butyldiphosphan, 1,2,3-Tri-tert-butyltriphosphan und Tetra-tert-butylcyclotetraphosphan |
| |
Authors: | M. Baudler,H. Tsch bunin |
| |
Affiliation: | M. Baudler,H. Tschäbunin |
| |
Abstract: | Contributions to the Chemistry of Phosphorus. 224. On the Thermolysis of 1,2-Di-tert-butyldiphosphane, 1,2,3-Tri-tert-butyltriphosphane, and Tetra-tert-butylcyclotetraphosphane On disproportionation of 1,2-di-tert-butyldiphosphane, H(t-Bu)P? P(t-Bu)H (1) , 1,2,3-tri-tert-butyltriphosphane, H2(t-BuP)3 (2) , is formed which reacts further at temperatures above 100°C to give 1-(tert-butylphosphino)-2,3,4-tri-tert-butylcyclotetraphosphan, P5(t-Bu)4H (4) . Compound 4 reacts with 1 or 2 with lengthening of the P-sidechain to furnish the corresponding 1-(1,2-di-tert-butyldiphosphino)-2,3,4-tri-tert-butylcyclotetraphosphane, P6(t-Bu)5H (5) . At temperatures above 170°C, 5 disproportionates into the tetra-tert-butylcyclotetraphosphane, (t-BuP)4 (3) which is stable up to about 200°C, and the bicyclo[3.1.0]hexaphosphane P6(t-Bu)4 from which the polycyclophosphanes P9(t-Bu)3 and P8(t-Bu)6 arise during the further course of the thermolysis. These products are finally converted through even more phosphorus-rich and more highly condensed t-butylcyclophosphanes into elemental phosphorus. In each reaction step, varying amounts of the monophosphane derivatives t-BuPH2, (t-Bu)2PH, and (t-Bu)3P are formed. The proposed course of the reaction is further substantiated by the pyrolysis products of pure 2 and 3 . |
| |
Keywords: | 1,2-Di-tert-butyldiphosphane 1,2,3-Tri-tert-butyltriphosphane Tetra-tert-butylcyclotetraphosphane 1-(tert-Butylphosphino)-2,3,4-tritert-butylcyclotetraphosphane 1-(1,2-Di-tert-butyldiphosphino)-2,3,4-tri-tert-butylcyclotetraphosbhane tert-Butylpolyphosphanes |
|
|