Citation: Lin-Jun ZHU, Tao HUANG, Teng ZHANG. Synthesis, Structure and Properties of an Iron Complex with Formally Zero Oxidation State[J]. Chinese Journal of Structural Chemistry, ;2022, 41(3): 220323. doi: 10.14102/j.cnki.0254-5861.2011-3339 shu

Synthesis, Structure and Properties of an Iron Complex with Formally Zero Oxidation State

Lin-Jun ZHU ^{a, b} ,
Tao HUANG ^a ,
Teng ZHANG ^{a, b,,}

a.
State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou 350002, China
b.
University of the Chinese Academy of Sciences, Beijing 100049, China

Corresponding author: Teng ZHANG, zhangteng@fjirsm.ac.cn
Received Date: 25 August 2021
Accepted Date: 8 October 2021

Figures(4)

An unusual iron complex with formally zero oxidation state, iron bis(6, 6΄-dimethyl-2, 2΄-bipyridine), was synthesized and its crystal structure was determined. Combination of experimental and theoretical studies reveals that the electronic structure of the complex is best described as Fe(Ⅱ)(Mebipy^-)₂ with anionic Mebipy^- ligands and high-spin Fe(Ⅱ) center.
- Fe(Mebipy)₂,
- crystal structure,
- electronic structure,
- redox-active ligand
1. [1]
  Bedford, R. B. How low does iron go? Chasing the active species in Fe-catalyzed cross-coupling reactions. Acc. Chem. Res. 2015, 48, 1485–1493. doi: 10.1021/acs.accounts.5b00042
2. [2]
  Chirik, P. J. Iron- and cobalt-catalyzed alkene hydrogenation: catalysis with both redox-active and strong field ligands. Acc. Chem. Res. 2015, 48, 1687–1695. doi: 10.1021/acs.accounts.5b00134
3. [3]
  Chakraborty, S.; Bhattacharya, P.; Dai, H.; Guan, H. Nickel and iron pincer complexes as catalysts for the reduction of carbonyl compounds. Acc. Chem. Res. 2015, 48, 1995–2003. doi: 10.1021/acs.accounts.5b00055
4. [4]
  Zhang, L.; Peng, D.; Leng, X.; Huang, Z. Iron-catalyzed, atom-economical, chemo- and regioselective alkene hydroboration with pinacolborane. Angew. Chem. Int. Ed. 2013, 52, 3676–3680. doi: 10.1002/anie.201210347
5. [5]
  Bianchini, C.; Giambastiani, G.; Luconi, L.; Meli, A. Olefin oligomerization, homopolymerization and copolymerization by late transition metals supported by (imino)pyridine ligands. Coord. Chem. Rev. 2010, 254, 431–455. doi: 10.1016/j.ccr.2009.07.013
6. [6]
  Yamamoto, A.; Morifuji, K.; Ikeda, S.; Saito, T.; Uchida, Y.; Misono, A. Diethylbis(bipyridine)iron. Butadiene cyclodimerization catalyst. J. Am. Chem. Soc. 2002, 90, 1878–1883.
7. [7]
  Sun, C. L.; Li, B. J.; Shi, Z. J. Direct C–H transformation via iron catalysis. Chem. Rev. 2011, 111, 1293–1314. doi: 10.1021/cr100198w
8. [8]
  Luo, Y.; Li, Y.; Yu, H.; Zhao, J. F.; Chen, Y. H.; Hou, Z. M.; Qu, J. P. DFT studies on the reduction of dinitrogen to ammonia by a thiolate-bridged diiron complex as a nitrogenase mimic. Organometallics 2012, 31, 335–344. doi: 10.1021/om200950q
9. [9]
  Bhutto, S. M.; Holland, P. L. Dinitrogen activation and functionalization using beta-diketiminate iron complexes. Eur. J. Inorg. Chem. 2019, 2019, 1861–1869. doi: 10.1002/ejic.201900133
10. [10]
  Figg, T. M.; Holland, P. L.; Cundari, T. R. Cooperativity between low-valent iron and potassium promoters in dinitrogen fixation. Inorg. Chem. 2012, 51, 7546–7550. doi: 10.1021/ic300150u
11. [11]
  Creutz, S. E.; Peters, J. C. Diiron bridged-thiolate complexes that bind N₂ at the Fe(Ⅱ)Fe(Ⅱ), Fe(Ⅱ)Fe(Ⅰ), and Fe(Ⅰ)Fe(Ⅰ) redox states. J. Am. Chem. Soc. 2015, 137, 7310–7313. doi: 10.1021/jacs.5b04738
12. [12]
  Creutz, S. E.; Peters, J. C. Catalytic reduction of N₂ to NH₃ by an Fe-N2 complex featuring a C-atom anchor. J. Am. Chem. Soc. 2014, 136, 1105– 1115. doi: 10.1021/ja4114962
13. [13]
  Kaes, C.; Katz, A.; Hosseini, M. W. Bipyridine: the most widely used ligand. A review of molecules comprising at least two 2, 2'-bipyridine units. Chem. Rev. 2000, 100, 3553–3590. doi: 10.1021/cr990376z
14. [14]
  Werner, A. Beitrag zur konstitution anorganischer verbindungen. Z. Anorg. Allg. Chem. 1899, 19, 158–178. doi: 10.1002/zaac.18990190114
15. [15]
  Werner, A. Über spiegelbild-isomerie bei eisenverbindungen. Ber. Dtsch. Chem. Ges. 1912, 45, 433–436. doi: 10.1002/cber.19120450165
16. [16]
  Willett, B. C.; Anson, F. C. Electrochemistry and adsorption of bis 2, 2'-bipyridinecobalt(Ⅰ) and bis 6, 6'-dimethyl-2, 2'-bipyridinecobalt(Ⅰ) in acetonitrile. J. Electrochem. Soc. 1982, 129, 1260–1266. doi: 10.1149/1.2124098
17. [17]
  Groshens, T. G.; Henne, B.; Bartak, D.; Klabunde, K. J. Metal vapor synthesis, chemical oxidation, and electrochemistry of bis(bipyridyl)cobalt(0)-preparation of bromide, tetracyanoethylene, and tetracyanoquinodimethane salts. Inorg. Chem. 1981, 20, 3629–3635. doi: 10.1021/ic50225a010
18. [18]
  Kaizu, Y.; Yazaki, T.; Torii, Y.; Kobayash, H. Electronic absorption spectra of zero-valent tris-(2, 2'-bipyridine) metal complexes. Bull. Chem. Soc. Jpn. 1970, 43, 2068–2071. doi: 10.1246/bcsj.43.2068
19. [19]
  Motten, A. G.; Hanck, K.; DeArmound, M. K. ESR of the reduction products of [Fe(bpy)₃]²⁺ and [Ru(bpy)₃]²⁺. Chem. Phys. Lett. 1981, 79, 541– 546. doi: 10.1016/0009-2614(81)85032-4
20. [20]
  Richert, S. A.; Tsang, P. K. S.; Sawyer, D. T. Ligand-centered redox processes for manganese, iron and cobalt, MnL3, FeL3, and CoL3, complexes (L = acetylacetonate, 8-quinolinate, picolinate, 2, 2'-bipyridyl, 1, 10-phenanthroline) and for their tetrakis(2, 6-dichlorophenyl)porphinato complexes [M(Por)]. Inorg. Chem. 2002, 28, 2471–2475.
21. [21]
  England, J.; Scarborough, C. C.; Weyhermüller, T.; Sproules, S.; Wieghardt, K. Electronic structures of the electron transfer series [M(bpy)₃]ⁿ, [M(tpy)₂]ⁿ, and [Fe(^tbpy)₃]ⁿ (M = Fe, Ru; n = 3+, 2+, 1+, 0, 1-): a mssbauer spectroscopic and DFT study. Eur. J. Inorg. Chem. 2012, 2012, 4605–4621. doi: 10.1002/ejic.201200232
22. [22]
  Hall, F. S.; Reynolds, W. L. Preparation of an iron(0) complex with 2, 2'-bipyridine. Inorg. Chem. 1966, 5, 931–932. doi: 10.1021/ic50039a046
23. [23]
  Herzog, S.; Klausch, U.; Lantos, J. Über die darstellung von tris-2, 2'-dipyridyl-kobalt(0) [CoDipy₃]. Zeitschrift. für. Chemie. 2010, 4, 150–150.
24. [24]
  Zhang, T.; Manna, K.; Lin, W. Metal-organic frameworks stabilize solution-inaccessible cobalt catalysts for highly efficient broad-scope organic transformations. J. Am. Chem. Soc. 2016, 138, 3241–3249. doi: 10.1021/jacs.6b00849
25. [25]
  Chan, B. C. K.; Baird, M. C. Reactions of 6, 6'-dimethyl-2, 2'-bipyridyl with iron(Ⅱ) in aqueous and non-aqueous media. Inorg. Chim. Acta 2004, 357, 2776–2782. doi: 10.1016/j.ica.2004.02.002
26. [26]
  Sheldrick, G. M. A short history of SHELX. Acta Crystallogr. A 2008, 64, 112–122. doi: 10.1107/S0108767307043930
27. [27]
  Frisch, M. J.; Trucks, G. W.; Schlegel, H. B.; Scuseria, G. E.; Robb, M. A.; Cheeseman, J. R.; Scalmani, G.; Barone, V.; Petersson, G. A.; Nakatsuji, H.; Li, X.; Caricato, M.; A. Marenich, V.; Bloino, J.; Janesko, B. G.; Gomperts, R.; Mennucci, B.; Hratchian, H. P.; Ortiz, J. V.; Izmaylov, A. F.; Sonnenberg, J. L.; Williams-Young, D.; Ding, F.; Lipparini, F.; Egidi, F.; Goings, J.; Peng, B.; Petrone, A.; Henderson, T.; Ranasinghe, D.; Zakrzewski, V. G.; Gao, J.; Rega, N.; Zheng, G.; Liang, W.; Hada, M.; Ehara, M.; Toyota, K.; Fukuda, R.; Hasegawa, J.; Ishida, M.; Nakajima, T.; Honda, Y.; Kitao, O.; Nakai, H.; Vreven, T.; Throssell, K.; Montgomery, Jr., J. A.; Peralta, J. E.; Ogliaro, F.; Bearpark, M. J.; Heyd, J. J.; Brothers, E. N.; Kudin, K. N.; Staroverov, V. N.; Keith, T. A.; Kobayashi, R.; Normand, J.; Raghavachari, K.; Rendell, A. P.; Burant, J. C.; Iyengar, S. S.; Tomasi, J.; Cossi, M.; Millam, J. M.; Klene, M.; Adamo, C.; Cammi, R.; Ochterski, J. W; . Martin, R. L.; Morokuma, K.; Farkas, O.; Foresman, J. B.; Fox, D. J. Gaussian 16, Gaussian, Inc., Wallingford CT 2016.
28. [28]
  Zhang, D.; Truhlar, D. G. Spin splitting energy of transition metals: a new, more affordable wave function benchmark method and its use to test density functional theory. J. Chem. Theory Comput. 2020, 16, 4416–4428. doi: 10.1021/acs.jctc.0c00518
29. [29]
  Lu, T.; Chen, F. Multiwfn: a multifunctional wavefunction analyzer. J. Comput. Chem. 2012, 33, 580–592. doi: 10.1002/jcc.22885
30. [30]
  Addison, C. C.; Davis, R.; Logan, N. Reaction of dirhenium decacarbonyl with dinitrogen tetroxide. Nitratopentacarbonylrhenium (Ⅰ). Inorg. Chem. 1967, 6, 1926–1927. doi: 10.1021/ic50056a040
31. [31]
  Mulliken, R. S. Electronic population analysis on Lcao-Mo molecular wave functions. 1. J. Chem. Phys. 1955, 23, 1833–1840. doi: 10.1063/1.1740588
32. [32]
  Mulliken, R. S. Electronic population analysis on Lcao-Mo molecular wave functions. 2. overlap populations, bond orders, and covalent bond energies. J. Chem. Phys. 1955, 23, 1841–1846. doi: 10.1063/1.1740589
33. [33]
  Mulliken, R. S. Electronic population analysis on Lcao-Mo molecular wave functions. 3. effects of hybridization on overlap and gross ao populations. J. Chem. Phys. 1955, 23, 2338–2342. doi: 10.1063/1.1741876
34. [34]
  Nalewajski, R. F.; Parr, R. G. Information theory, atoms in molecules, and molecular similarity. Proc. Natl. Acad. Sci. USA. 2000, 97, 8879–8882. doi: 10.1073/pnas.97.16.8879
35. [35]
  Hirshfeld, F. L. Bonded-atom fragments for describing molecular charge-densities. Theor. Chim. Acta 1977, 44, 129–138. doi: 10.1007/BF00549096
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