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  Three-Coordinate Iron(0) Complexes with N-Heterocyclic Carbene and Vinyltrimethylsilane Ligation: Synthesis, Characterization, and Ligand Substitution Reactions

Cheng, J., Chen, Q., Leng, X., Ye, S., & Deng, L. (2019). Three-Coordinate Iron(0) Complexes with N-Heterocyclic Carbene and Vinyltrimethylsilane Ligation: Synthesis, Characterization, and Ligand Substitution Reactions. Inorganic Chemistry, 58(19), 13129-13141. doi:10.1021/acs.inorgchem.9b02009.

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Cheng, Jun1, Author
Chen, Qi1, Author
Leng, Xuebing1, Author
Ye, Shengfa2, Author           
Deng, Liang1, Author
Affiliations:
1State Key Laboratory of Organometallic Chemistry, Center for Excellence in Molecular Synthesis, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, 345 Lingling Road, Shanghai, 200032, PR China, ou_persistent22              
2Research Group Ye, Max-Planck-Institut für Kohlenforschung, Max Planck Society, ou_2541708              

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 Abstract: Low-coordinate iron(0) species are implicated as intermediates in a range of iron-catalyzed organic transformations. Isolable iron(0) complexes with coordination numbers of less than four, however, are rarely known. In continuing with our interests in three-coordinate iron(0) complexes with N-heterocyclic carbene (NHC) and alkene ligation, we report herein the synthesis and ligand substitution reactivity of three-coordinate iron(0) complexes featuring monodentate alkene ligands, [(NHC)Fe(η2-vtms)2] (vtms = vinyltrimethylsilane, NHC = 1,3-bis(2′,6′-diisopropylphenyl)-imidazol-2-ylidene (IPr), 1; 1,3-bis(2′,6′-diisopropylphenyl)-4,5-tetramethylene-imidazol-2-ylidene (cyIPr), 2; 1,3-bis(2′,6′-diisopropylphenyl)-4,5,6,7-tetrahydro-1,3-diazepin-2-ylidene (7-IPr), 3). Complexes 1–3 were synthesized from the one-pot reactions of ferrous dihalides with the N-(2,6-diisopropylphenyl)-substituted NHC ligands, vtms, and KC8. Reactivity study of 1 revealed its facile ligand substitution reactions with terminal aryl alkynes, ketones, isocyanides, and CO, by which iron(0) complexes [(IPr)Fe(η2-HCCAr)] (Ar = Ph, 5; p-CH3C6H4, 6; 3,5-(CF3)2C6H3, 7), [(IPr)Fe(η2-OCPh2)2] (8), [(IPr)Fe(CNR)4] (R = 2,6-Me2C6H3, 9; But, 10), and (IPr)Fe(CO)4 (11) were prepared in good yields. These iron(0) complexes have been characterized by 1H NMR, solution magnetic susceptibility measurement, single-crystal X-ray diffraction study, 57Fe Mössbauer spectroscopy, and elemental analysis. Characterization data and computational studies suggest S = 1 ground-spin states for three-coordinate iron(0) complexes 1–3 and 5–8 and S = 0 ground states for 9–11. Theoretical studies on the three-coordinate complexes 1, 6, and 8 indicated pronounced metal-to-ligand backdonation from occupied Fe 3d orbitals to the π* orbitals of the C═C, C≡C, and C═O moieties of the π ligands. In addition, 1 proved an effective precatalyst for the cyclotrimerization reaction of alkynes.

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Language(s): eng - English
 Dates: 2019-07-062019-09-192019-10-07
 Publication Status: Published in print
 Pages: 13
 Publishing info: -
 Table of Contents: -
 Rev. Type: Peer
 Identifiers: DOI: 10.1021/acs.inorgchem.9b02009
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Title: Inorganic Chemistry
  Abbreviation : Inorg. Chem.
Source Genre: Journal
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Publ. Info: Washington, DC : American Chemical Society
Pages: - Volume / Issue: 58 (19) Sequence Number: - Start / End Page: 13129 - 13141 Identifier: ISSN: 0020-1669
CoNE: https://pure.mpg.de/cone/journals/resource/0020-1669