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Reaction of the cyclotetraphosphane (PCF 3 ) 4  or of a mixture of (PCF 3 ) 4  and (PCF 3 ) 5  with 2,3-dimethyl-1,3-butadiene or isoprene at 25 °C leads to the [4 + 2]-cycloadducts of bis(trifluoromethyl) diphosphene and the phospholene derivatives 2a and 2b, respectively, in the molar ratio diphosphinine/phospholene = 1/2. The analogous reactions of the cycloarsanes (AsCF 3 ) 4,5  give the Diels/Alder compounds 4 and 5 of bis(trifluoromethyl)diarsene in 90% yield without arsolene formation. Cyclopentadiene, 1,3-cyclohexadiene and cis or trans piperylene do not react with (AsCF 3 ) 4,5 , up to temperatures of 60 °C. However, the corresponding [4 + 2]-cycloadducts 6 - 8 are produced by irradiation of the reaction mixture with UV light. The novel phospholenes 2a and 2b as well as the diarsinines 4 - 8 have been characterized by spectroscopic data (MS, NMR, IR). 2a was coordinated as a phosphane ligand to the pentacarbonylchromium fragment by reaction with the photochemically generated complex Cr(CO) 5  · THF to afford the new compound(3).

zeitschrift für naturforschung b

Neue Phospha- und Arsa-Heterocyclen aus Cyclophosphanen bzw. -arsanen (ECF 3 ) n  (E = P, As; n = 4, 5) und 1,3-Dienen / Novel Phospha- and Arsa-Heterocycles from Cyclophosphanes or -arsanes (ECF 3 ) n  (E = P, As; n = 4, 5) and 1,3-Dienes