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Characterization and Reactivity of Isocyanide Complexes of Manganese

Hans Juergen Mueh

出版	University of Wisconsin--Madison, 1976
URL	http://books.google.com.hk/books?id=epHOAAAAMAAJ&hl=&source=gbs_api

註釋

A series of complexes Mn(RNC)6(+) (R = a monosubstituted phenyl ring) were prepared by reaction of MnI2 or Mn(CO)5X (X = Cl, Br) with the free ligand. A correlation coefficient of 0.98 was obtained. Attempted oxidation of Mn(C6H5NC)5Cl with AgPF6 in THF resulted in the preparation of Mn(C6H5NC)6(+)PF6( - ). The complex Mn(p-CH3C6H4NC)4(CO)Cl reacted with AgPF6 in a series of complexing solvents, producing the complexes (Mn(p-CH3C6H4NC)4(CO)(L))PF6 (L = p-CH3C6H4NC, C5H5N, CH3NC, (CH3)3CNC, and o-CH3C6H4NH2). A correlation coefficient of 0.99 was obtained. Isomeric complexes cis- and trans-(Mn(CO)2(CH3NC)4)(+) and fac- and mer-(Mn(CO)3(CH3NC)3)(+) were synthesized. Ultraviolet irradiation of CpMn(CO)3 in THF with excess isocyanide produced the complexes CpMn(RNC)3 (R = CH3, C6Cl5, C6H5, p-ClC6H4). A series of complexes Mn2(CO)(10-x)(RNC)(x) (x = 1,2,4,5; R = CH3, C6H5, p-ClC6H4) was prepared thermally and by nucleophilic attack of Mn(CO)(5-x)(RNC)(x)X with Mn(CO)5( - ). The complexes Mn(C6H5NC)5X (X = Cl, Br, CN, SnCl3) were also prepared and examined electrochemically.