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Updated: Jun 30, 2026

Atomic Scale Structural Studies of Macromolecular Assemblies by Solid-state Nuclear Magnetic Resonance Spectroscopy
Published on: September 17, 2017
Nature of Cr-NO Bonding from 15N Solid-State NMR and X-ray Absorption Spectroscopic Signatures
Yuya Kakiuchi1, Svetlana Shapovalova2, Alexander Guda2
1Department of Chemistry and Applied Biosciences, ETH Zürich, Vladimir Prelog Weg 2, Zürich CH-8093, Switzerland.
Abstract:
Transition metal-nitrosyl species holds prime importance in chemistry, yet describing their bonding remains a great challenge. Envisioning to develop a spectroscopic descriptor that addresses nitrosyl electronic structure, 15N solid-state NMR (ssNMR) spectroscopy, augmented by computational analysis, is herein applied to probe and disentangle the bonding in a family of low-valent Cr-nitrosyl complexes. Combined with complementary techniques (scXRD, IR, and X-ray absorption spectroscopy) pointing at a significant π-back-donation, 15N ssNMR-assisted orbital analysis highlights the formation of filled π(Cr-N) orbitals. Bonding analysis, anchored on spectroscopic data, reveals an increased Cr-N bond order reminiscent of a potential Cr-N multiple-bond character, which revisits the known analogy between nitrosyl and imido/nitrido ligands. Further analysis hints to a non-negligible influence of ancillary ligand, where strong σ-donor enhances Cr-N π-bonding. The sensitive response to the nitrosyl bonding and the ease to record 15N ssNMR signature and its link to the underlying electronic structures makes it privilege descriptor to understand metal-nitrosyl bonding at molecular (orbital) level.
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