A non-metal-to-metal I+−Ag+ coordination bond

Rakesh Puttreddy (), Niklas Limberg, Carsten Müller, Sebastian Riedel (), Antonio Frontera, Jan Lundell and Kari Rissanen ()
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Rakesh Puttreddy: University of Jyvaskyla
Niklas Limberg: Freie Universität Berlin
Carsten Müller: Freie Universität Berlin
Sebastian Riedel: Freie Universität Berlin
Antonio Frontera: Universitat de les Illes Balears
Jan Lundell: University of Jyvaskyla
Kari Rissanen: University of Jyvaskyla

Nature Communications, 2025, vol. 16, issue 1, 1-9

Abstract: Abstract Metal-metal bonds between metal cations are ubiquitous in coordination complexes, whereas similar bonding characteristics between non-metal and metal cations are not. Here, we report an X-ray crystal structure of a centrosymmetric complex [Ag(m-O3SCF3)2{(4MePyNO)2I}]2 (1-AgI), where the iodine(I) cation forms an unusual 3-centre 4-electron [O–I–O]+ halogen bond with two oxygen atoms from two 4-methylpyridine N-oxide (4MePyNO). The iodine(I) atoms from two [4MePyNO−I−ONPyMe4]+ cations, which, together with the two silver(I) atoms from the paddlewheel [Ag(m-O3SCF3)2]22− structure, establish two unique I+–Ag+ bonds at 2.863(2) Å. This bond length is characteristic of bimetallic coordination bonds such as Au+−Ag+ [2.8553(6) Å], Cu+−Ag+ [2.8616(9) Å], and Pt2+−Ag+ [2.8602(4) Å]. Density Functional Theory calculations unambiguously support the existence of the I+–Ag+ coordination bond between non-metal and metal cations in complex 1-AgI.

Date: 2025
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DOI: 10.1038/s41467-025-62191-1

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