A Stable Homoleptic Organometallic Iron(IV) Complex
(2020) In Chemistry - A European Journal 26(56). p.12728-12732- Abstract
A homoleptic organometallic FeIV complex that is stable in both solution and in the solid state at ambient conditions has been synthesized and isolated as [Fe(phtmeimb)2](PF6)2 (phtmeimb=[phenyl(tris(3-methylimidazolin-2-ylidene))borate]−). This FeIV N-heterocyclic carbene (NHC) complex was characterized by 1H NMR, HR-MS, elemental analysis, scXRD analysis, electrochemistry, Mößbauer spectroscopy, and magnetic susceptibility. The two latter techniques unequivocally demonstrate that [Fe(phtmeimb)2](PF6)2 is a triplet FeIV low-spin S=1 complex in the ground state, in agreement with quantum chemical calculations. The... (More)
A homoleptic organometallic FeIV complex that is stable in both solution and in the solid state at ambient conditions has been synthesized and isolated as [Fe(phtmeimb)2](PF6)2 (phtmeimb=[phenyl(tris(3-methylimidazolin-2-ylidene))borate]−). This FeIV N-heterocyclic carbene (NHC) complex was characterized by 1H NMR, HR-MS, elemental analysis, scXRD analysis, electrochemistry, Mößbauer spectroscopy, and magnetic susceptibility. The two latter techniques unequivocally demonstrate that [Fe(phtmeimb)2](PF6)2 is a triplet FeIV low-spin S=1 complex in the ground state, in agreement with quantum chemical calculations. The electronic absorption spectrum of [Fe(phtmeimb)2](PF6)2 in acetonitrile shows an intense absorption band in the red and near IR, due to LMCT (ligand-to-metal charge transfer) excitation. For the first time the excited state dynamics of a FeIV complex was studied and revealed a ≈0.8 ps lifetime of the 3LMCT excited state of [Fe(phtmeimb)2](PF6)2 in acetonitrile.
(Less)
- author
- organization
- publishing date
- 2020-10-06
- type
- Contribution to journal
- publication status
- published
- subject
- keywords
- high-valent iron, N-heterocyclic carbenes, organometallic complexes, photophysics, transient absorption spectroscopy
- in
- Chemistry - A European Journal
- volume
- 26
- issue
- 56
- pages
- 5 pages
- publisher
- Wiley-Blackwell
- external identifiers
-
- scopus:85090602033
- pmid:32369645
- ISSN
- 0947-6539
- DOI
- 10.1002/chem.202002158
- language
- English
- LU publication?
- yes
- id
- 990d6300-74c6-40c6-86e9-fce93ef65490
- date added to LUP
- 2020-10-02 12:11:53
- date last changed
- 2024-09-20 06:06:16
@article{990d6300-74c6-40c6-86e9-fce93ef65490, abstract = {{<p>A homoleptic organometallic Fe<sup>IV</sup> complex that is stable in both solution and in the solid state at ambient conditions has been synthesized and isolated as [Fe(phtmeimb)<sub>2</sub>](PF<sub>6</sub>)<sub>2</sub> (phtmeimb=[phenyl(tris(3-methylimidazolin-2-ylidene))borate]<sup>−</sup>). This Fe<sup>IV</sup> N-heterocyclic carbene (NHC) complex was characterized by <sup>1</sup>H NMR, HR-MS, elemental analysis, scXRD analysis, electrochemistry, Mößbauer spectroscopy, and magnetic susceptibility. The two latter techniques unequivocally demonstrate that [Fe(phtmeimb)<sub>2</sub>](PF<sub>6</sub>)<sub>2</sub> is a triplet Fe<sup>IV</sup> low-spin S=1 complex in the ground state, in agreement with quantum chemical calculations. The electronic absorption spectrum of [Fe(phtmeimb)<sub>2</sub>](PF<sub>6</sub>)<sub>2</sub> in acetonitrile shows an intense absorption band in the red and near IR, due to LMCT (ligand-to-metal charge transfer) excitation. For the first time the excited state dynamics of a Fe<sup>IV</sup> complex was studied and revealed a ≈0.8 ps lifetime of the <sup>3</sup>LMCT excited state of [Fe(phtmeimb)<sub>2</sub>](PF<sub>6</sub>)<sub>2</sub> in acetonitrile.</p>}}, author = {{Prakash, Om and Chábera, Pavel and Rosemann, Nils W. and Huang, Ping and Häggström, Lennart and Ericsson, Tore and Strand, Daniel and Persson, Petter and Bendix, Jesper and Lomoth, Reiner and Wärnmark, Kenneth}}, issn = {{0947-6539}}, keywords = {{high-valent iron; N-heterocyclic carbenes; organometallic complexes; photophysics; transient absorption spectroscopy}}, language = {{eng}}, month = {{10}}, number = {{56}}, pages = {{12728--12732}}, publisher = {{Wiley-Blackwell}}, series = {{Chemistry - A European Journal}}, title = {{A Stable Homoleptic Organometallic Iron(IV) Complex}}, url = {{http://dx.doi.org/10.1002/chem.202002158}}, doi = {{10.1002/chem.202002158}}, volume = {{26}}, year = {{2020}}, }