Perchlorate and difluorophosphate coordination derivatives of manganese carbonyl

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Abstract
The complexes Mn(CO)5(OClO3) and Mn(CO)3L2(OClO3) (L = PPh3, P(OPh)3; L2 = bpy*) are formed by abstraction reactions with AgClO4 from the corresponding bromo complexes in dichloromethane. The perchlorato complexes have been characterized by i.r. and mass spectroscopy. They undergo facile substitution reactions in which the perchlorato group is replaced by halide ions (X- = Cl, Br, I), phosphines [PR3 (R = Ph, p- tolyl, m-tolyl), dpe, dpm]* or solvent molecules (MeCN, PhCN, MeOH, Me2CO, py*). Reaction with fluoride ion yields Mn(CO)3F3 plus other decomposition products. When Mn(CO)5X and Mn(CO)3L2X (X = Br) are made to react with AgPF6 in dichloromethane, hydrolysis of the PF6- ion occurs to yield the corresponding difluorophosphato complexes (X = PO2F2-), which have been characterized by i.r., 19F N.M.R. and mass spectroscopy. They are reasonably stable at low temperatures, but decompose at room temperature. The difluorophosphato group is more inert than perchlorato with the rate of substitution decreasing in the order CO ≈ PPh3 > bpy > P(OPh)3.

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