Preparation of new (η5-C5H4CH3)Mn(NO)(PPh3) and (η7-C7H7)Mo(CO)-(PPh3) complexes |
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Authors: | DL Reger DJ Fauth MD Dukes |
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Institution: | Department of Chemistry, University of South Carolina, Columbia, South Carolina 29208 U.S.A. |
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Abstract: | The complex (η5-C5H4CH3)Mn(NO)(PPh3)I has been prepared by the reaction of NaI with (η5-C5H4CH3)Mn(NO)(CO)(PPh3)]+ and also by the reaction of (η5-C5H4CH3)Mn(NO)(CO)2]+ with NaI followed by PPh3. This iodide compound reacts with NaCN to yield (η5-C5H4CH3)Mn(NO)(PPh3)CN which is ethylated by (C2H5)3O]BF4 to yield (η5-C5H4CH3)Mn(NO)(PPh3)(CNC2H5)]+. Both (η5-C5H4CH3)Mn(NO)(CO)2]+ and (η5-C5H4CH3)Mn(NO)(PPh3)(CO)]+ react with NaCN to yield (η5-C5H4CH3)Mn(NO)(CN)2]?. This anion reacts with Ph3SnCl to yield cis-(η5-C5H4CH3)Mn(NO)(CN)2SnPh3 and with (C2-H5)3O]BF4 to yield (η5-C5H4CH3)Mn(NO)(CNC2H5)2]+. The reaction of (η5-C5-H4CH3)Mn(NO)(PPh3)I with AgBF4 in acetonitrile yields (η5-C5H4CH3)Mn-(NO)(PPh3)(NCCH3)]+. The complex (η5-C5H4CH3)Mn(NO)(CO)I, produced in the reaction of (η5-C5H4CH3)Mn(NO)(CO)2]+ with NaI, is not stable and decomposes to the dimeric complex (η5-C5H4CH3)2Mn2(NO)3I for which a reasonable structure is proposed. Similar dimers can be prepared from the other halide salts. The reaction of (η7-C7H7)Mo(CO)(PPh3)I with NaCN yields (η7-C7-H7)Mo(CO)(PPh3)CN which is ethylated by (C2H5)3O]BF4 to yield (η7-C7H7)-Mo(CO)(PPh3)(CNC2H5)]+. The interaction of this molybdenum halide complex with AgBF4 in acetonitrile and pyridine yields (η7-C7H7)Mo(CO)(PPh3)-(NCCH3)]+ and (η7-C7H7)Mo(CO)(PPh3)(NC5H5)]+, respectively. Both (η5-C5-H4CH3)Mn(NO)(PPh3)I and (η7-C7H7)Mo(CO)(PPh3)I are oxidized by NOPF6 to the respective 17-electron cations in acetonitrile at ?78°C but revert to the neutral halide complex at room temperature. This result is supported by electrochemical data. |
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