2014
DOI: 10.1002/anie.201405673
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Cleavage and Formation of Molecular Dinitrogen in a Single System Assisted by Molybdenum Complexes Bearing Ferrocenyldiphosphine

Takamasa Miyazaki,
Hiromasa Tanaka,
Yoshiaki Tanabe
et al.

Abstract: The N≡N bond of molecular dinitrogen bridging two molybdenum atoms in the pentamethylcyclopentadienyl molybdenum complexes that bear ferrocenyldiphosphine as an auxiliary ligand is homolytically cleaved under visible light irradiation at room temperature to afford two molar molybdenum nitride complexes. Conversely, the bridging molecular dinitrogen is reformed by the oxidation of the molybdenum nitride complex at room temperature. This result provides a successful example of the cleavage and formation of molec… Show more

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Cited by 126 publications
(94 citation statements)
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References 49 publications
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“…An FT-IR spectrum of unlabeled 2 has ap eak at 1042 cm À1 (KBr), and is close to that of aterminal nitride-Mo complex reported previously,(h 5 -C 5 Me 5 )Mo( 14 N)(depf) (depf = 1,1'-bis(diethylphosphinoferrocene) (n Mo 14 N = 1024 cm À1 ;F igures S7 and S8). [26] TheF T-IR spectrum of 15 N-2 has a n Mo15N band at 1010 cm À1 (KBr), which is good agreement with the calculated value (n Mo 15 N = 1011 cm À1 ). AU V-vis spectrum of 2 in THF has three bands at 366 (shoulder peak), 402 (e = 350 cm À1 m À1 ), and 504 nm (e = 231 cm À1 m À1 ;F igure S8), which correspond well to the TD-DFT-calculated absorption spectrum of 2 in the closed-shell singlet state.T hese bands are assigned to amixture of d-d transition and MLCT bands on the basis of the theoretical calculation (see Figures S32 and S33, and Table S6).…”
mentioning
confidence: 75%
“…An FT-IR spectrum of unlabeled 2 has ap eak at 1042 cm À1 (KBr), and is close to that of aterminal nitride-Mo complex reported previously,(h 5 -C 5 Me 5 )Mo( 14 N)(depf) (depf = 1,1'-bis(diethylphosphinoferrocene) (n Mo 14 N = 1024 cm À1 ;F igures S7 and S8). [26] TheF T-IR spectrum of 15 N-2 has a n Mo15N band at 1010 cm À1 (KBr), which is good agreement with the calculated value (n Mo 15 N = 1011 cm À1 ). AU V-vis spectrum of 2 in THF has three bands at 366 (shoulder peak), 402 (e = 350 cm À1 m À1 ), and 504 nm (e = 231 cm À1 m À1 ;F igure S8), which correspond well to the TD-DFT-calculated absorption spectrum of 2 in the closed-shell singlet state.T hese bands are assigned to amixture of d-d transition and MLCT bands on the basis of the theoretical calculation (see Figures S32 and S33, and Table S6).…”
mentioning
confidence: 75%
“…16e, 17 However, there has been no successful example of catalytic nitrogen fixation via direct cleavage of molecular dinitrogen as a key step under ambient reaction conditions until now.…”
Section: Introductionmentioning
confidence: 99%
“…These parameters were further corroborated by acquisition and analysis of pulse X-band Davies electron nuclear double resonance (ENDOR) spectra and pulse Qband field-swept EPR spectra (see the Supporting Information). Additional small hyperfine couplings were observed in the Davies ENDOR spectra (see the Supporting Information) to 1 H( j A x,y,z j= [10,18,10] MHz), assigned to the two proximal protons from the arene ligand, and 35/37 Cl (j A x,y,z j = [10.5, 10.5, 10.5] MHz). Computationally determined Mulliken spin densities and the large observed hyperfine coupling Isosurfacesa re shown at the 0.05 e À3 level and orbital energies (relative to the HOMO) are provided.…”
mentioning
confidence: 99%