Reactions of Trivalent Iodine Reagents with Classic Iridium and Rhodium Complexes

Abstract

In this work, the reactions of iodine (III)

Synthesis of cationic gold(III) complexes using iodine(III)

“…Direct reaction of PPh3 with 5R resulted in oxidation of the phosphine, generating dication 18, previously reported by Burford from halide abstraction/coordination reactions at chlorophosphonium cations. [12][13][14] Based on these results, we hypothesized that scrambling is induced by the presence of a halide substituent, and have investigated the reactions of selected halide-free phosphine or NHC containing Au(I) complexes as well as N-bound Au(I) complexes with 5R (Figure 1). The results show that oxidized phosphine and/or scrambling were observed in all phosphine-containing Au(I) complexes reactions.…”

Reactions of PhIX2 I(iii) oxidants with heavy triphenyl pnictines

“…Clear crystals where grown by a vapour diffusion of hexane/cloroform. Yield 0.468 g 79 % 1 H NMR (400 MHz, CDCl3): δ 7.82 (t, 4H), 7.73 (t, 4H), 7.64 (t, 1H); 19…”

“…We initially viewed these reactions as indicating that I(III) oxidants are incompatible with phosphine ligands, although have since found they are compatible when the phosphine is bound to a metal in some cases. 19 In light of Burford's work on heavier pnictogen(V) dications described above, we wondered if these I(III) dications could be an effective reagent for their generation, circumventing the steps involving halogenation/halide abstraction.…”

Weiss’ Reagents: A synthetically useful class of iodine(III) coordination compounds

“…49 The generation of 38 through simple aquo reactivity differs markedly from the generally employed synthetic approach for Au(III)-OH formation which relies on alkali metal or silver salt metathesis reactivity at a Au(III) chloride. 50 54 The outcomes for reactions involving 4-DMAP ligated Weiss' Reagent are shown in Scheme 17. In all these examples complex product distributions arose from the occurrence of ligand and anion scrambling, which has also been reported for other organometallic systems employing I(III) oxidants, and seems to be dependent on the presence of chloride as either ligand or counter-ion.…”