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Low Coordinated Phosphorus Compounds, 28. Monophosphabutadiens
Appel, Rolf,Knoch, Falk,Kunze, Holger
, p. 3151 - 3159 (2007/10/02)
Reactions of organylbis(trimethylsilyl)phosphanes 1a-c with α,β-unsaturated acyl chlorides 2a, b and β-chlorovinyl ketones 3a, b yield 1,2,3,4-tetrahydro-1,2-diphosphinines 5a-h.Their sulfurisation leads to the corresponding disulfides 7a,b,e,f.On the contrary, 1d reacts with 2a and 3a to yield the 1,2-diphosphetanes 6i,j.Their structure is affirmed by x-ray structure determination of 6i.Only the introduction of the bulky 2,4,6-tri-tert-butylphenyl group in the reaction of 1e with 2a leads to the isolation of the 1-phosphabutadiene 4k.Reactions of the α,β-unsaturated phosphane 8 with acyl chlorides 9a,b yield the 2-phosphabutadienes 10a,b.The spontaneous formation of the 1,2-diphosphinines 5a-h and 1,2-diphosphetanes 6i,j as well as the stability of the 2-phosphabutadienes 10a,b is discussed.
