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Persistent four-coordinate iron-centered radical stabilized by ?-donation.

ABSTRACT: Dinuclear iron carbonyl complex 2, which contains an elongated unsupported Fe-Fe bond, was synthesized by the reaction between Fe₂(CO)₉ and phosphinyl radical 1. Thermal Fe-Fe bond homolysis led to the generation of a four-coordinate carbonyl-based iron-centered radical, 3, which is stabilized by ?-donation. Complex 3 exhibited high reactivity toward organic radicals to form diamagnetic five-coordinate Fe(ii) complexes.

SUBMITTER: Sunada Y

PROVIDER: S-EPMC5515065 | biostudies-literature | 2016 Jan

REPOSITORIES: biostudies-literature

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Persistent four-coordinate iron-centered radical stabilized by π-donation.

Sunada Yusuke Y Ishida Shintaro S Hirakawa Fumiya F Shiota Yoshihito Y Yoshizawa Kazunari K Kanegawa Shinji S Sato Osamu O Nagashima Hideo H Iwamoto Takeaki T

Chemical science 20150925 1

Dinuclear iron carbonyl complex 2, which contains an elongated unsupported Fe-Fe bond, was synthesized by the reaction between Fe2(CO)9 and phosphinyl radical 1. Thermal Fe-Fe bond homolysis led to the generation of a four-coordinate carbonyl-based iron-centered radical, 3, which is stabilized by π-donation. Complex 3 exhibited high reactivity toward organic radicals to form diamagnetic five-coordinate Fe(ii) complexes. ...[more]

PMID: 28758000

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Project description:The electronic structures of the four- and five-coordinate aryl-substituted bis(imino)pyridine iron dinitrogen complexes, ((iPr)PDI)FeN(2) and ((iPr)PDI)Fe(N(2))(2) ((iPr)PDI = 2,6-(2,6-(i)Pr(2)-C(6)H(3)-N=CMe)(2)C(5)H(3)N), have been investigated by a combination of spectroscopic techniques (NMR, Mössbauer, X-ray Absorption and X-ray Emission) and DFT calculations. Homologation of the imine methyl backbone to ethyl or isopropyl groups resulted in the preparation of the new bis(imino)pyridine iron dinitrogen complexes, ((iPr)RPDI)FeN(2) ((iPr)RPDI = 2,6-(2,6-(i)Pr(2)-C(6)H(3)-N=CR)(2)C(5)H(3)N; R = Et, (i)Pr), that are exclusively four coordinate both in the solid state and in solution. The spectroscopic and computational data establish that the ((iPr)RPDI)FeN(2) compounds are intermediate spin ferrous derivatives (S(Fe) = 1) antiferromagnetically coupled to bis(imino)pyridine triplet diradical dianions (S(PDI) = 1). While this ground state description is identical to that previously reported for ((iPr)PDI)Fe(DMAP) (DMAP = 4-N,N-dimethylaminopyridine) and other four-coordinate iron compounds with principally ?-donating ligands, the d-orbital energetics determine the degree of coupling of the metal-chelate magnetic orbitals resulting in different NMR spectroscopic behavior. For ((iPr)RPDI)Fe(DMAP) and related compounds, this coupling is strong and results in temperature independent paramagnetism where a triplet excited state mixes with the singlet ground state via spin orbit coupling. In the ((iPr)RPDI)FeN(2) family, one of the iron SOMOs is essentially d(z2) in character resulting in poor overlap with the magnetic orbitals of the chelate, leading to thermal population of the triplet state and hence temperature dependent NMR behavior. The electronic structures of ((iPr)RPDI)FeN(2) and ((iPr)PDI)Fe(DMAP) differ from ((iPr)PDI)Fe(N(2))(2), a highly covalent molecule with a redox non-innocent chelate that is best described as a resonance hybrid between iron(0) and iron(II) canonical forms as originally proposed in 2004.

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Persistent four-coordinate iron-centered radical stabilized by ?-donation.

Publications

Persistent four-coordinate iron-centered radical stabilized by π-donation.

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