ISSN:
0009-2940
Keywords:
Chemistry
;
Inorganic Chemistry
Source:
Wiley InterScience Backfile Collection 1832-2000
Topics:
Chemistry and Pharmacology
Description / Table of Contents:
Contributions to the Chemistry of Phosphorus, 131. Synthesis and Properties of the Methylenediphosphiranes (t-BuP)2)C = CR2 (R = H, Me, 4-ClC6H4)The first methylenediphosphiranes (diphosphamethylenecyclopropanes) (t-BuP)2C = CH2 (1), (t-BuP)2C = CMe2 (2), and (t-BuP)2C = C(4-ClC6H4)2 (3) were synthesized by [2 + 1] cyclocondensation of K(t-Bu)P - P(t-Bu)K with the corresponding 1,1-dichloroolefins. The homocyclophosphanes (t-BuP)n (n = 4,3) and in the case of 1 mainly H(t-Bu)P - P(t-Bu)H are formed as by-products. The three-membered heterocycles 2 and 3 could be purely isolated as surprisingly stable compounds. According to an X-ray single-crystal analysis 3 possesses approximately C2 symmetry and exhibits one of the smallest bonding angles ψ (P - P - C) = 52.4° on a phosphorus atom experimentally proved so far. Along [100] there are canals filled with disordered n-pentane molecules.
Notes:
Die ersten Methylendiphosphirane (Diphosphamethylencyclopropane) (t-BuP)2C = CH2 (1), (t-BuP)2C = CMe2 (2) und (t-BuP)2C = C(4-ClC6H4)2 (3) wurden durch [2 + 1]-Cyclokondensation von K(t-Bu)P - P(t-Bu)K mit den entsprechenden 1,1-Dichlorolefinen synthetisiert. Als Nebenprodukte entstehen die Homocyclophosphane (t-BuP)n (n = 4,3) und im Fall von 1 vor allem H(t-Bu)P - P(t-Bu)H. Die Dreiringheterocyclen 2 und 3 konnten als thermisch überraschend beständige Verbindungen in reiner Form isoliert werden. 3 besitzt nach der Röntgenstrukturanalyse annähernd die Symmetrie C2 und enthält mit ψ (P - P - C) = 52.4° einen der kleinsten experimentell gesicherten Bindungswinkel am Phosphor. Längs [100] liegen fehlgeordnet mit n-Pentan gefüllte Kanäle vor.
Additional Material:
2 Ill.
Type of Medium:
Electronic Resource
URL:
http://dx.doi.org/10.1002/cber.19841170422
