Das erste kinetisch stabile gemischt‐substituierte Cyclotriphosphin (III) wird durch [2 + l]‐Cyclokondensation des Diphosphids (I) mit dem Phosphindichlorid (II) synthetisiert.
Das erste kinetisch stabile gemischt‐substituierte Cyclotriphosphan, 1,2‐Di‐tert‐butyl‐3‐iso‐propyl‐cyclotriphosphan, (PBut)2(PPri) (1), wurde durch [2+1]‐Cyclokondensation von K(But)P–P(But)K mit PriPCl2 in n‐Pentan synthetisiert. Als Nebenprodukte entstehen vor allem (PBut)4 sowie gemischt‐substituierte Cyclotetra‐ und Cyclopentaphosphane. 1 konnte durch Hochvakuumdestillation in reiner Form isoliert und vollständing charakterisiert werden. Es bildet zwei Diastereomere, von denen das beständigere mit cis‐ständiger tert‐Butyl‐ und iso‐Propylgruppe unter Inertgas bei Raumtemperatur tagelang haltbar ist. Bei der Thermolyse von 1 entstehen unter anderem die gemischt‐substituierten Cyclotetraphosphane (PBut)2(PPri)2 (2) und (PBut)3(PPri) (3), dern 31P‐NMR‐Parameter mitgeteilt werden.
The first three-membered P2AS heterocycle, tri-tert-butyl-diphosphaarsa-cyclopropane (tri-tert-butyl-diphosphaarsirane) (1) was synthesized by [2+1] cyclocondensation of K(t-Bu)P-P(t-Bu)K with t-BuAsCl2 in n-pentane at - 78 °C. Tetra-tert-butyl-1,2-di-phospha-3,4-diarsa-cyclobutane (2), tetra-tert-butyl-triphosphaarsa-cyclobutane (3) as well as (t-BuP)4 and five-membered cycloarsaphosphanes are also formed. The diphospha-arsa-cyclopropane 1 could be isolated in a pure state. It forms two diastereomers, of which the isomer with trans-orionted tert-butyl groups at the phosphorus atoms is the most stable. The 31P NMR parameters of the four-membered cycloarsaphosphanes 2 and 8 are reported
Abstract The first three-membered P2Sb heterocycle, tri-tert-butyl-diphosphastiba-cyclopropane (tri-tert-butyl-diphosphastibirane) (1) was synthesized by [2+1] cyclocondensation of K(t-Bu)P-P(t-Bu)K with t-BuSbCl2 in n-pentane at -78 °C. Tetra-tert-butyl-1,2-diphospha- 3,4-distiba-cyclobutane (2), tetra-tert-butyl-triphosphastibacyclobutane (3) as well as (t-BuP)4 and five-membered cyclostibaphosphanes are also formed. Because of its hyperreactivity, 1 could not be isolated in a pure state. It forms two diastereomers, of which the isomer with trans-oriented tert-butyl groups at the phosphorus atoms is the more stable one. The 31P NMR parameters of the four-membered cyclostibaphosphanes 2 and 3 are reported.
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