130322-18-8Relevant academic research and scientific papers
Synthesis of the phosphorus-carbon double bond by reaction between pentacarbonylchromium or -tungsten complexes of phosphinidenes and carbenes. Application to the synthesis of the 1,2-dihydrophosphete ring
Huy, Ngoc Hoa Tran,Ricard, Louis,Mathey, Fran?ois
, p. 1791 - 1795 (2008/10/08)
The condensation of a carbene complex R1R2C=M(CO)5 with a transient terminal phosphinidene complex [RP=M(CO)5] (M = Cr, W) primarily yields a phosphaalkene complex, R1R2C=P(R)→M(CO)5, which, in some cases, dimerizes. This method has been applied to the synthesis of Ph2C=P(Ph)→W(CO)5 which is stable as a monomer. When a vinylcarbene complex such as PhCH=CH-C(OEt)=Cr(CO)5 is reacted with (phenylphosphinidene)pentacarbonyltungsten, the transient phosphabutadiene complex thus obtained instantly undergoes a [2 + 2] cyclization to give a (1,2-dihydrophosphete(P-W))pentacarbonyltungsten complex. The X-ray crystal structure analysis of this complex [C22H17O6PW, fw 592.20; space group P1 (No. 2) with a = 10.519 (1) ?, b = 10.887 (1) ?, c = 11.134 (1) ?, α = 112.78 (2)°, β = 98.15 (2)°, γ = 97.13 (2)°; V = 1141.18 (68) ?3; Z = 2; d(calcd) = 1.723 g cm-3] confirms the presence of the four-membered ring with a very long P-C sp3-intracyclic bond [1.902 (5) ?]. It proved possible to convert this complex into the corresponding P-oxide without breaking the ring.
