714264-19-4Relevant academic research and scientific papers
Transformation of acyclic alkenes to hydrido carbynes by (PNP R)Re complexes
Ozerov, Oleg V.,Watson, Lori A.,Pink, Maren,Caulton, Kenneth G.
, p. 6363 - 6378 (2004)
Synthesis of (PNPR)ReOCl2 (PNPR = (R 2PCH2SiMe2)2N, R = iPr, Cy, and tBu) from (Me2S)2-ReOCl3 and (PNPR)MgCl is described. Magnesium and H2 convert (PNPR)ReOCl2 first to (PNPR)ReO(H)2 and then to (PNPR)Re(H)4, the last being an operationally unsaturated species which can bind PMe3 or p-toluidine. Acyclic alkenes react with (PNPR)Re(H)4 at 22 °C to give first (PNPR)Re(H)2(olefin) and then (PNP R)ReH(carbyne), in equilibrium with its η2-olefin adduct. Re can also migrate to the terminal carbon of internal olefins to form a carbyne complex. Allylic C-SiMe3 or C-NH2 bonds are not broken, but OEt, OPh, and F vinyl substituents (X) are ultimately cleaved from carbon to give the Re≡C-CH3 complex and liberate HX. DFT calculations, together with detection of intermediates for certain olefins, help to define a mechanism for these conversions.
