PREPARATION OF NEW (ETA5-C5H4CH3)MN(NO)(PPH3) AND CETA-7-C7H7)MO(CO)-(PPH3) COMPLEXES

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. © 1979.