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Comparing the Electronic Structure of Iron, Cobalt, and Nickel Compounds That Feature a Phosphine-Substituted Bis(imino)pyridine Chelate

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Title
Comparing the Electronic Structure of Iron, Cobalt, and Nickel Compounds That Feature a Phosphine-Substituted Bis(imino)pyridine Chelate
Author(s)
Mena, Matthew R.; Jun-Hyeong Kim; Sangho So; Ben-Daat, Hagit; Porter, Tyler M.; Ghosh, Chandrani; Sharma, Anuja; Flores, Marco; Groy, Thomas L.; Mu-Hyun Baik; Trovitch, Ryan J.
Publication Date
2022-05
Journal
Inorganic Chemistry, v.61, no.17, pp.6438 - 6450
Publisher
American Chemical Society
Abstract
© It was recently discovered that (Ph2PPrPDI)Mn (PDI = pyridine diimine) exists as a superposition of low-spin Mn(II) that is supported by a PDI dianion and intermediate-spin Mn(II) that is antiferromagnetically coupled to a triplet PDI dianion, a finding that encouraged the synthesis and electronic structure evaluation of late first row metal variants that feature the same chelate. The addition of Ph2PPrPDI to FeBr2 resulted in bromide dissociation and the formation of [(Ph2PPrPDI)FeBr][Br]. Reduction of this precursor using excess sodium amalgam afforded (Ph2PPrPDI)Fe, which possesses an Fe(II) center that is supported by a dianionic PDI ligand. Similarly, reduction of a premixed solution of Ph2PPrPDI and CoCl2 yielded the cobalt analog, (Ph2PPrPDI)Co. EPR spectroscopy and density functional theory calculations revealed that this compound features a high-spin Co(I) center that is antiferromagnetically coupled to a PDI radical anion. The addition of Ph2PPrPDI to Ni(COD)2 resulted in ligand displacement and the formation of (Ph2PPrPDI)Ni, which was found to possess a pendent phosphine group. Single-crystal X-ray diffraction, CASSCF calculations, and EPR spectroscopy indicate that (Ph2PPrPDI)Ni is best described as having a Ni(II)-PDI2- configuration. The electronic differences between these compounds are highlighted, and a computational analysis of Ph2PPrPDI denticity has revealed the thermodynamic penalties associated with phosphine dissociation from 5-coordinate (Ph2PPrPDI)Mn, (Ph2PPrPDI)Fe, and (Ph2PPrPDI)Co.
URI
https://pr.ibs.re.kr/handle/8788114/11746
DOI
10.1021/acs.inorgchem.2c00008
ISSN
0020-1669
Appears in Collections:
Center for Catalytic Hydrocarbon Functionalizations(분자활성 촉매반응 연구단) > 1. Journal Papers (저널논문)
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