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By M. Bacci, J. Fischer, M.H. Gubelmann, B. Koren, F. Mathey, M. Melnik, J.H. Nelson, P. Sivy, F. Valach, A.F. Williams

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Other reports of reactions with carbonyl compounds and their derivatives with (Ph3P)2PtO2 include ketones, aldehydes and oximes375) and oximes376). adiketones can add two (PhaP)PtO2 molecules to give a light-sensitive complex containing two five membered cycles377). (Ph3P)2PtO2 reacts with aromatic diketones of the type ArCOCOAr to give acid anhydrides ArCOOCOAr, and with acid anhydrides to give acid peroxides ArCOOOCOAr 378). 1,1,1-trifluoroacetone reacts with (Ph3)2PtO2 similarly to acetone, but somewhat faster.

7 b) it will be seen that the HOMO is the ~r~(±) orbital lying perpendicular to the MO2 plane. Norman zSO suggested that the structure of the r/1 : r/2 complex [(Ph3P)2C1RhOz]2 (Fig. 2) could be considered as two pyramidal (Ph3P)2C1RhO2 molecules in which the ~r~(l) of one dioxygen is attacking the Rh of the other pyramid. ) orbital has a nodal plane between the two oxygen atoms) and the direction of attack will be perpendicular to the Dioxygen Complexes of the Transition Metals 37 MO2 plane and (ii) the changes in bond length in comparison with the simple ~2 complex (PhaP)3CIRhO256) show the oxygen atom bound to both rhodium atoms to move away from the first rhodium, whereas the other oxygen atom moves closer to the rhodium: + E ~ Rh_ k o .

There is considerable variation of reactivity between different structural types and within a given structural type, but one general feature of the reactivity of dioxygen complexes may usefully be mentioned before discussing each structural type. The binding of dioxygen to a transition metal is accompanied (i) by a reduction of the number of unpaired electrons on the oxygen (to one or zero) and (ii) by the transfer of charge density to the dioxygen. As a result of the first effect the kinetic barrier to spin changes in reactions of dioxygen is eliminated, and as a result of the second, the dioxygen tigand acquires basic or nucleophilic character.

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Transition Metal Complexes Structures and Spectra by M. Bacci, J. Fischer, M.H. Gubelmann, B. Koren, F. Mathey, M. Melnik, J.H. Nelson, P. Sivy, F. Valach, A.F. Williams

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