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The electronic structure of a β-diketiminate manganese hydride dimer

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Title
The electronic structure of a β-diketiminate manganese hydride dimer
Author(s)
Changjin Oh; Joëlle Siewe; Thao T. Nguyen; Airi Kawamura; Marco Flores; Thomas L. Groy; John S. Anderson; Ryan J. Trovitch; Mu-Hyun Baik
Subject
Azomethine, ; Ligands, ; Single Crystals
Publication Date
2020-11
Journal
DALTON TRANSACTIONS, v.49, no.41, pp.14463 - 14474
Publisher
ROYAL SOC CHEMISTRY
Abstract
© The Royal Society of Chemistry. The electronic structure of a dimeric manganese hydride catalyst supported by β-diketiminate ligands, [(2,6-iPr2PhBDI)Mn(μ-H)]2, was investigated with density functional theory. A triple bond between the manganese centres was anticipated from simple electron-counting rules; however, calculations revealed Mn-Mn Mayer bond orders of 0.21 and 0.27 for the ferromagnetically-coupled and antiferromagnetically-coupled extremes, respectively. In accordance with experimentally determined Heisenberg exchange coupling constants of -15 ± 0.1 cm-1 (SQUID) and -10.2 ± 0.7 cm-1 (EPR), the calculated J0 value of -10.9 cm-1 confirmed that the ground state involves antiferromagnetic coupling between high spin Mn(ii)-d5 centres. The effect of steric bulk on the bond order was examined via a model study with the least sterically-demanding version of the β-diketiminate ligand and was found to be negligible. Mixing between metal- and β-diketiminate-based orbitals was found to be responsible for the absence of a metal-metal multiple bond. The bridging hydrides give rise to a relatively close positioning of the metal centres, while bridging atoms possessing 2p orbitals result in longer Mn-Mn distances and more stable dimers. The synthesis and characterization of the bridging hydroxide variant, [(2,6-iPr2PhBDI)Mn(μ-OH)]2, provides experimental support for these assessments. This journal i
URI
https://pr.ibs.re.kr/handle/8788114/7559
DOI
10.1039/d0dt02842h
ISSN
1477-9226
Appears in Collections:
Center for Catalytic Hydrocarbon Functionalizations(분자활성 촉매반응 연구단) > 1. Journal Papers (저널논문)
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