ISSN:
0009-2940
Keywords:
Cyclocotrimerization
;
Selenophosphinites
;
Alkynes, activated
;
Selenophenes
;
Chemistry
;
Inorganic Chemistry
Source:
Wiley InterScience Backfile Collection 1832-2000
Topics:
Chemistry and Pharmacology
Notes:
Selenophosphinito complexes (OC)4Mn(η2-Se\documentclass{article}\usepackage{amsmath}\pagestyle{empty}\begin{document}$ \dddot - $\end{document}PR21) (2a, b) [R1 = cyc-Hex (a), tBu (b)] are formed by the reaction of BrMn(CO)5 with the phosphane selenides R21HPSe (1a, b) in the presence of the auxiliary base Et(iPr)2N. According to an X-ray structural analysis, 2a crystallizes in the space group \documentclass{article}\pagestyle{empty}\begin{document}$ P\bar 1 $\end{document} with Z = 2. The dimeric complex [(OC)4Mn(μ-Se\documentclass{article}\usepackage{amsmath}\pagestyle{empty}\begin{document}$ \dddot - $\end{document}PMe2)]2 (4c) is not obtained in a straightforward way. Compound 4c is only obtained via the intermediate Br(OC)4Mn-Se\documentclass{article}\usepackage{amsmath}\pagestyle{empty}\begin{document}$ \dddot - $\end{document}P(H)Me2 (3c) by HBr elimination with nBuLi. Complex 3c is formed by replacement of carbon monoxide in BrMn(CO)5 by Me2HPSe (1c). A dissociative equilibrium between [(OC)4 Mn(μ-Se\documentclass{article}\usepackage{amsmath}\pagestyle{empty}\begin{document}$ \dddot - $\end{document}PMe2)]2 (4c) and the monomeric species (OC)4Mn(\documentclass{article}\usepackage{amsmath}\pagestyle{empty}\begin{document}$ \dddot - $\end{document}2-Se\documentclass{article}\usepackage{amsmath}\pagestyle{empty}\begin{document}$ \dddot - $\end{document}PMe2) was not observed. The cyclocotrimerization of the 〉P\documentclass{article}\usepackage{amsmath}\pagestyle{empty}\begin{document}$ \dddot - $\end{document}Se function with the activated alkynes ZC≡CZ [Z = CO2R2; R2 = Me (d), Et (e), iPr (f), cyc-Hex (g)] was successful only in the case of the cyclohexyl derivative 2a to give the selenaphosphamanganabicycloheptadienes 5d - g. An X-ray structural analysis proved that 5d crystallizes in the space group \documentclass{article}\pagestyle{empty}\begin{document}$ P\bar 1 $\end{document} with Z = 2. Under CO pressure 5d was degraded to the selenophene 6.
Additional Material:
2 Ill.
Type of Medium:
Electronic Resource
URL:
http://dx.doi.org/10.1002/cber.19961290811
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