Oxidative addition of iodine

Oxidative-addition of iodine also was investigated for the complex C -bzimAu]3. This complex behaves like most of the CTCs since it adds iodine at only one gold center to yield [p,-N, C -bzimAu]3l2 [59]. The X-ray structure shows that it consists of discrete trinuclear units with the three gold atoms bridged by 1 -benzylimidazolates. 

The oxidative addition of iodine to diorganotellurides has also been examined by stopped-flow spectroscopy. The initial fast reaction of iodine with diphenyltellur-ide (23), di-4-methoxyphenyltelluride (24), A,V-dimethyl-2-(aminomethyl)phenyl-telluride (17), and 2,6-di-tert-butyltelluropyran-4-one (25) displays inverted Arrhenius behavior (negative values of E ), which is consistent with a preequilibrium involving higher-order iodine species as shown in equation (6). The I4 species is the actual oxidant for diorganotellurides as shown in equation (7). Thus, the initial reaction is formation of the r i-association complex of I4 with the... 

An alternative route to an unsaturated Si4 ring involves the oxidative addition of iodine to the tetrahedral tetrasilane R4Si4 (R = Si Bu3) (Scheme 10.10). ... 

The biscarbene complexes were found (142) from their H-NMR spectra to be mixtures of geometrical isomers, due to hindered rotation about the C—N or C—O bonds, and the isomers have been separated by fractional crystallization in the case of [Au C(0Et)NHC6H4Me 2]+C10. Treatment of these species with triphenylphosphine gave mixed ligand complexes and formamidines [Eq. (39)]. They also underwent oxidative addition of iodine to yield the first gold(III) carbene complexes. 

As for palladium discussed above, the majority of platinacyclopentanes are based on the divalent metal. However, the structurally characterised complex [Pt(C4H8) (Ph)I(bipy)] 91 has been obtained by treating [Pt(C4H8)(bipy)] 85 with di-phenyliodonium triflate followed by triflate-iodide metathesis [Eq. (36)]. As in the palladium example 79 described above, both cis and trans oxidative addition products are observed.103 Prior to this, the structurally characterised platinum(IV) derivative [Pt(C4H8)I2(PMe2Ph)2] 92 had been obtained via trans oxidative addition of iodine to [Pt(C4H8)(PMe2Ph)2] [Eq. (37)].113... 

Oxidative addition of iodine 14. 10.3.2.1.1 Reaction with organic peroxides and other dichalcogenides 14, 10.3.2.2.1 Reaction with dipnictogenides 14, 10.3.2.2.1... 

The presence of the co-ordinated hydroxy-groups was confirmed from i.r. and thermogravimetric data. Oxidative addition of iodine to [Pt(acac)2], either in the solid state or in carbon tetrachloride solution, has yielded the black complex [Pt(acac)2l2]- U.v.-visible and mass spectral measurements show the reaction to be reversible in solution or in the gas phase, and a singlecrystal X-ray analysis (Table 8) indicates trans octahedral geometry for the product. 

Bis(trifluoromethyl)platinum complexes may conveniently be prepared by the reaction of dimethyl(cyclo-octa-l,5-diene)platinum with trifluoro-iodomethane in methylene chloride, followed by displacement of the cydo-octadiene with the required ligand L (L = AsMcs, PMeaPh, pyridine, RNC, etc.) Oxidative addition of iodine thence gives the platinum(iv) compounds ... 

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