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Insertion Reactions of [ReH(CO)5–n(PMe3)n] Complexes (n = 2–4) with aldehydes, CO2, and activated acetylenes

✍ Scribed by Daniel Nietlispach; Dario Veghini; Heinz Berke

Publisher
John Wiley and Sons
Year
1994
Tongue
German
Weight
853 KB
Volume
77
Category
Article
ISSN
0018-019X

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✦ Synopsis

Me3P

Me3P PMe, 1 2 3 stereoisomers which display hydride/PMe, cis-and hydride/CO trans-configurations.

The syntheses of 2 and 3 were recently reported [5], and 1 was obtained in high yield by reduction of [ReCl(CO),(PMe,),] with Na in THF and subsequent acidification with H,O.

Out of the series of compounds 1-3, only 3 reacted with benzaldehyde in toluene to yield a benzyloxy complex 4 (Eqn. 1) which was isolated as pale yellow 0,-sensitive crystals in 89% yield. Note, that alkoxide complexes of the type [Re(OR)(CO),L,] were prepared earlier by Bergman and Simpson [6] by non-insertive reaction paths.

The 'H-NMR spectrum of 4 shows, among other resonances, a characteristic 9 at 4.59 ppm, and the ',C('H)-NMR spectrum reveals a quint. at 76.7 ppm. Both absorptions correspond to 'H or I3C signals of the CH, group, which are shifted to lower field with respect to those of free benzyl alcohol (ds('H) = 0.06 ppm, d6(I3C) = I 1.3 ppm). From the quinf. coupling pattern of the CHI and the CO resonances and a sin the ,'P-NMR spectrum, the 'equatorial' arrangement of the P-substituents in 4 is deduced.

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