Deutsch Intern
    Prof. Dr. W. A. Schenk

    Sulfur Oxides

    Early work on the coordination chemistry of the sulfur oxides began with carbonyl-SO2 complexes of chromium, molybdenum, and tungsten [13, 18, 19, 22, 30] (see Metal Carbonyls). Our main interest was the interrelationship between structure, spectroscopy, and the various bonding modes of SO2.

     

    Molecular Structure of [Cr(CO)5(SO2)] [18]
    Molecular Structure of [Mo(CO)2(PMe3)3(eta2-SO2)] [30]
    Structure of the cation of [Cp*Ru(PMe3)2(eta2-H2C=SO2)]PF6 [62]

    Our work on the coordination chemistry of sulfur monoxide began with the isolation of the square-planar compounds [MCl(PR3)2(SO)] (M = Rh, Ir) which had been synthesized using thiirane-1-oxide as an SO-transfer reagent. These were the first mononuclear complexes of sulfur monoxide to be rigorously characterized, including a crystal structure determination [24].

     

    Structure of the cation of [Cp*Ru(PMe3)2(h2-O=SO2)]PF6 [73]
    Molecular Structure of [IrCl(Pi-Pr3)2(SO)] [24]

    Later came a few halfsandwich-type complexes of iron and ruthenium [32, 43, 46, 58]. Typical reactions of these species are the oxidation of the coordinated SO to SO2 [31], coordinative and oxidative addition at iridium [25, 36], the liberation and trapping of SO [35], and one example of a [3+2]-cycloaddition [58].

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