Journal article
Leveraging Chelating Amido Ligands to Support Metal-Metal Bonding in Dinuclear Cr(II) Complexes
Inorganic chemistry
03/05/2026
DOI: 10.1021/acs.inorgchem.6c00424
PMCID: PMC12997166
PMID: 41784549
Abstract
Herein, we report a series of Cr(II) complexes containing triaryl, tetradentate ligands derived from o-phenylenediamide that illuminate how rigid, chelating amido ligands facilitate Cr–Cr bonding. The aminolysis reaction of Cr[N(SiMe3)2]2(thf)2 with H2(L1)─a protonated N4 proligand containing flanking NMe2 groups─yielded square planar and mononuclear Cr(L1) (1), whereas the same reaction with N2S2 and N2O2 proligands with flanking SMe and OMe groups yielded dinuclear [Cr(L2)]2 (2) and [Cr(L3)]2 (3). The structures of 2 and 3 revealed Cr–Cr distances of 2.3356(6) and 2.3481(5) Å, consistent with metal–metal bonding, which was confirmed by the complete active space methods. The theoretical results suggest that Cr–Cr bonding is assisted by the chelating nature of the bridging amido ligands, which fold the dinuclear structure and orient the metals so that side-on overlap of Cr 3d orbitals can occur. Variable-temperature SQUID magnetometry and spectroscopic data (e.g., UV–vis-NIR, Raman, and IR) reported for 1–3 show differences indicative of the change in nuclearity and electronic structure. Collectively, these results reveal bridging amido ligand characteristics that support metal–metal bonding with Cr(II), and they help account for the wide range of metal–metal distances observed in dinuclear (or binuclear) Cr(II) complexes containing Cr2N2 cores.
Details
- Title: Subtitle
- Leveraging Chelating Amido Ligands to Support Metal-Metal Bonding in Dinuclear Cr(II) Complexes
- Creators
- Janadhi L Ananda Nakath Durage - Department of Chemistry, The University of Iowa, Iowa City, Iowa 52442, United StatesJoan Cardona - University of IowaSoumen Sinhababu - Colorado State UniversityDarby H Duffy - University of IowaDaniel Martinez - University of IowaMatthew P Shores - Colorado State UniversityDaniel K Unruh - University of IowaBess Vlaisavljevich - University of IowaScott R Daly - University of Iowa
- Resource Type
- Journal article
- Publication Details
- Inorganic chemistry
- DOI
- 10.1021/acs.inorgchem.6c00424
- PMID
- 41784549
- PMCID
- PMC12997166
- NLM abbreviation
- Inorg Chem
- ISSN
- 1520-510X
- eISSN
- 1520-510X
- Publisher
- American Chemical Society
- Grant note
- Ministerio de Ciencia e Innovacisup3;n: TED2021-129593B-I00 National Science Foundation: CHE-1956399
J.L.A., D.D., D.M., and S.R.D. thank the NSF for support (CHE-2247235). J.C.O. thanks the Ministerio de Ciencia e Innovacion (project TED2021-129593B-I00). XRD data were collected using the instrument supported by NSF CHE-1828117. S.S. and M.P.S. thank the NSF (CHE-1956399) and Colorado State University for support of magnetic measurements carried out at the CSU Analytical Research Core facility (RRID: SCR_021758). Some of the computations supporting this project performed on high-performance computing systems were made possible by resources funded by NSF award OAC-1626516.
- Language
- English
- Electronic publication date
- 03/05/2026
- Academic Unit
- Core Research Facilities; Chemistry
- Record Identifier
- 9985141988902771
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