The unique bonding and the variety of structures presented by metal-olefin compounds have provided the stimulus for recent study of this class of compounds. Although many aspects of the bonding and structure of these compounds are still obscure, several general methods have been developed for their synthesis. The following series of preparations deals with the metal-olefin compounds containing more than one double bond in the hydrocarbon moiety. These preparations illustrate methods that may readily be adapted to the preparation of a number of metal-olefin compounds in which the hydrocarbon is a diolefin. (11) 2KzPtC14 + C4Hs -+ K2(C13PtC4H,PtC13) + 2KC1 Chatt' has prepared and investigated this complex and presented evidence to show that the butadiene acts as a bridging group between two PtC1,-units. The present preparation represents a slight modification of his procedure particularly with regard to the control of the acidity of the potassium tetrachloroplatinate(I1) solution.
Procedure
A. POTASSIUM HEXACHLOROp-1,4-BUTADIENE-DIPLATINATEOne gram of dry potassium tetrachloroplatinate(I1) $ is dissolved in 15 ml. of 5 '% hydrochloric acid. The container is thoroughly flushed with gaseous butadiene and then charged with butadiene to a pressure of 100 cm. The pres-
Temp, for dehydration, °C. Ni2 + Ni(glycine)2-2H20 795 2.12 2.72 135 ~140 Cu2 + CuS04'5H20 875 1.98 2.75 220Cr3 +[Cr(ox)2(H20)2]K-3 965 2.02 2.66 High H20 1012 2.72 increases in the same order. As is shown by the M-OH2 and O-H-O distances, the effects of coordination and hydrogen bonding are also increasing in the same order. Therefore we conclude that a cooperative effect of coordination and hydrogen bonding is responsible for the shift of the band and the rise of temperature of dehydration.Although the vibrational mode of the band is not yet determined, it is attributable to either one of the modes among wagging, twisting and rocking vibrations. A detailed study of the nature of this band is now in progress and will be reported later together with the measurements in the KBr region.Acknowledgment.-The authors wish to express their sincere thanks to Mr. N. Ooi of the Sumitomo Chemical Company for aid in obtaining the spectra.
The reactions of some organoiodides with isomeric ew-bis(tolyl)bis(pyridine)platinum(Il) were investigated. In all of the reactions at least one tolyl group was displaced and this displacement was usually accompanied by an addition of the organoiodide resulting in a platinum)IV) compound. The reaction of allyl iodide with either the o-tolyl or p-tolyl derivative produced the identical compound (CsH6N)2Pt( C3Hs)2(I3)2, apparently a six-coordinated platinum(IV) complex. The ultraviolet spectrum of this compound indicates the presence of the triiodide ion and the nmr spectrum of the allyl group favors a -bonded configuration.
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