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The preparation of 21 -oxa, 21 -thia-, 21,23-dioxa-, 21,23-dithia-, and 21 -oxa-23-thia-porphins is described.tThese new porphin analogues have spectral properties similar to those of the porphins. which supports their formulation as aromatic macrocycles. Surprising basicity is displayed by 21.22-and 21.23-dioxaporphins and unusual mass spectra are produced by the oxaporphins. Only the 21 -oxa-and 21 -thia-porphins form metal complexes under the usual conditions used for rnetalloporphin formation. The results of deuterium exchange studies on the new macrocycles are reported.METAL complexes of porphins and dihydroporphins theoretical and experimental study. The porphins

Trifluoromethyl iodide reacts with [AuMeL] to give [AuMe,(CF,)L] and [AulL] (L = PMe, or PMe,Ph), or [Au-(CF,)L] and Me1 (L = PPh,), or a mixture of these products ( L = PMePh,). In some cases reaction of [AuMe-(PMe,)] with CF,I gives [AuMe(CF,) I (PMe,)].Evidence is presented that the reactions proceed, a t least in part, L69 3BXby a free-radical chain mechanism.REACTIONS of methyl iodide with the complexes [AuMeL] (L = PMe,, PMePh, PMePh,, or PPh,) have been reported previou~ly.l-~ In all cases the initial reaction took place according to equation (l), the products arising from rapid methyl for halogen exchange between the product of oxidative addition of [AuMeL] with MeI, namely cis-[AuMe,IL] and unchanged [AuMeL] [equation ( 2)]. However, a slower subsequent reaction then took cis-[AuMe,IL] + [AuMeL] place which was dependent on the nature of the ligand L.Thus when L = PPh, the complex [AuMe,L] underwent reductive elimination of ethane to give ultimately the products of equation (3), while when L = PMe, or

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