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Addition of CH3S03F or CH3S03CF3 to IrCl(CO)(PPh3)2 results in the highly labile oxidative addition product IrCl(CO)-(PPh3)2(CH3)(X) (X= S03F or S03CF3). Substitution of various anions for S03F" or S03CF3" provides a convenient route to a series of Ir(III) complexes which are inaccessible via direct oxidative addition. The iridium(III) complexes prepared by this route are of type 4 with X = F, Cl, Br, I, ACS,MX), N3, ONO, N03,CH3C00, S202C7H7, (7VC)2Pt(CN)2, and7VCC(CN)2. Vibrational and nmr spectroscopies establish that X is trans to CH3 and triphenylphosphines are mutually trans. In several cases the mode of linkage to the metal (indicated above by the italic element) was determined.

4) This structuie determination was performed by Drs. Frenz and Troup of Molecular Structure Corp., College Station, Texas 77840. The unit cell is monoclinic with extinctions hOI, I = 2n + 1, and O M ) , k = 2n + 1 indicating the space group R 1 / c . Cell constants are a = 7.680 (2) A, b The presence of four molecules in the unit cell gives a reasonable density, 1.895 g/cm3. A Syntex P i automatic diffractometer with Mo K a radiation was employed to collect 1904 independent reflections via the 8-28 scan technique. The three Fe atoms were located by a Patterson map and nonhydrogen atoms were found in succeeding Fourier syntheses. A total of 1440 independent reflections having fo2 > 3 0 f .~ were used for refinement of a trial structure. Anisotropic thermal parameters were included for iron while C and 0 were refined isotropically and hydrogen atoms were not included. On the final cycle of least-squares refinement R, = 0.061 and R2 = 0.085. McGraw-Hill, New York, N.Y., 1969, p 161 ff. = 16.363 (3) a, = 13.936 (2) A, = 900, p = 103.55 (2)0, = 900.

reagents in organic chemistry,1 their utilization in inorganic chemistry has been limited. Eaborn and coworkers have observed that CH3S03F reactions with metal complexes lead to alkylation of coordinated cyanide, S03F--C1metathesis, and oxidation.2 More unusual, however, is the possibility of generating new cationic metal-alkyl complexes such as those reported here.An excess of CH3SOsF (25.0 mmol) is stirred with 6.18 X 10-1 mmol of Vaska's compound, IrCl(CO)-(PPh3)2, in dry air-free benzene (60 ml) at room temperature until the color is completely dissipated (1-2 hr). A white solid, IrCl(C0)(PPh3)2(CH3)(S03F),3 is then isolated from benzene-heptane. In DCC13 solution the nmr exhibits a triplet for the methyl group (t 8.93, /p_h = 7 Hz, area 3) and an unresolved phenyl proton resonance (r 2.68, area 33). The high vCo (2064 cm-1, Nujol mull) indicates a simple oxidative addition product;4 indeed Eaborn and coworkers list it as such.2 However, as shown below, the compound is ionic and is therefore quite unlike the usual oxidative addition products of Vaska's compound, such as IrCl(CO)(PPh3)2(CH3)I, which typically are six-coordinate, substitution-inert, molecular species. The molecular weight in HCC13, 884, agrees with a molecular or an ion pair formulation (caled 894). In a more polar solvent, nitromethane, its conductance, 71 ohm-1 cm2 mol-1, is characteristic of a 1:1 electrolyte. The observed vco, 2062 cm-1, confirms that the compound still contains a formal Ir(III) oxidation state in this solvent. High conductivity and high vco, 2062 cm-1, also are observed for a solution in acetonitrile. The unsolvated IrCl(CO)(PPh3)2(CH3)-(

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