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Abstract
The work herein describes the synthesis of five three-coordinate silver(I) complexes comprising a bidentate ligand L1, either bpy (2,2′-bipyridyl) or bpyMe2 (4,4′-dimethyl-2,2′-dipyridyl), and a monodentate ligand L2, either mtz (1-methyl-1H-1,2,3-triazole), 4-Etpy (4-ethylpyridine), or 4-DMAP (N,N-dimethylpyridin-4-amine). Upon reaction of the three-coordinate silver(I) complexes with 0.5 equiv of I2, the reactions quantitatively produce a 1:1 pair of complexes of a four-coordinate silver(I) complex [Ag(L1)2]PF6 and a two-coordinate iodonium complex [I(L2)2]PF6. The combination of [Ag(bpyMe2)2]PF6 and [I(4-DMAP)2]PF6 gave rise to an I+···Ag+ interaction where the I+ acts as a nucleophile, only the second example of which, that was observed in both the solution (NMR) and solid (X-ray) states.
Highlights
The pursuit of new halonium ion motifs has been ongoing since their popularization in the 1990s,1−4 three decades after first being described in the literature,5,6 which was fueled by Barluenga using his reagent [I(pyridine)2]BF4 (Barluenga’s reagent) to demonstrate their great utility toward a myriad of organic transformations such as the electrophilic iodonation of unactivated arenes, the promotion of C−C and C−X bond formation, and the selective direct iodonation of peptides.7−9
Article combined with the quantum theory of “atoms-in-molecules” (QTAIM), the noncovalent interaction plot (NCIPlot) index, and the natural bond orbital (NBO) analyses
The first examples of heteroleptic halonium complexes highlighted that halonium ions can,21−24 if suitable ligands are present, undergo ligand scrambling in solution
Summary
The pursuit of new halonium ion motifs has been ongoing since their popularization in the 1990s,1−4 three decades after first being described in the literature, which was fueled by Barluenga using his reagent [I(pyridine)2]BF4 (Barluenga’s reagent) to demonstrate their great utility toward a myriad of organic transformations such as the electrophilic iodonation of unactivated arenes, the promotion of C−C and C−X bond formation, and the selective direct iodonation of peptides.−. While three-coordinate silver(I) complexes are not as common as their two- and four-coordinate counterparts, they are still well accounted for in the literature.− their use as precursors toward the synthesis of halonium ions via cation exchange was only recently reported, opening up the possibility of a new pool of potential silver(I) precursors that could be used to synthesize desirable halonium complexes The derivatives of this first example of a three-coordinate silver(I) complex successfully reacting to a combination of a halonium ion and a silver(I) complex, by what could be described as a partial cation exchange, demonstrated a highly interesting and previously unknown interaction in which the I+ was acting as a nucleophile toward the Ag+ (I+···Ag+ = 3.4608(3) Å; Figure 1). Article combined with the quantum theory of “atoms-in-molecules” (QTAIM), the noncovalent interaction plot (NCIPlot) index, and the natural bond orbital (NBO) analyses
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