The reaction of Ph2PCH2CH(R)CN (R = H, CH3) and M(CO)6 (M = Cr, Mo, W) with an excess of NaBH4 in ethanol provides excellent yields of cis-coordinated(CO)4M[(Ph)2PCH2CH(R)CH2NH2] complexes. Phosphorus nmr spectra of the reaction mixtures indicate that the products arise from phosphine containing precursors. These precursors have been isolated and identified as the phosphine-imidate complexes, (C0)4M[(Ph)2PCH2CH(R)C(OC2H5)NH]. The corresponding phosphine-amine complexes are obtained when these complexes are subsequently reduced with NaBH4. This suggests that the nitrile groups have been activated toward reduction by nucleophilic attack by ethanol on the CN carbons. Reactions of (CO)4W[(C6H5)2PCH2CH(CH3) CH2NH2] and (CO)4W[(C6H5)2P(CH2)2C(0C2H5)NH] with (C6H5)3P and (C6H5)P(CH3)2 indicated that the nitrogen portion of the bidentate ligand can be replaced by phosphorus. For (C6H5)P(CH3),-r-both replacement reactions were complete within 48 h providing a cis/trans ratio of ca. 1.5.
| Identifer | oai:union.ndltd.org:BSU/oai:cardinalscholar.bsu.edu:handle/182641 |
| Date | January 1982 |
| Creators | Akhavan, Sepehra |
| Contributors | Storhoff, Bruce N. |
| Source Sets | Ball State University |
| Detected Language | English |
| Format | viii, 53 leaves ; 28 cm. |
| Source | Virtual Press |
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