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Volumn 124, Issue 46, 2002, Pages 13842-13855

Spectroscopic and computational studies on [(PhTttBu)2Ni2(μ-O)2]: Nature of the Bis-μoxo (Ni3+)2 "diamond" core

Author keywords

[No Author keywords available]

Indexed keywords

ABSORPTION; ACTIVATION ENERGY; COMPUTATIONAL METHODS; DIMERS; ELECTRONIC STRUCTURE; PROBABILITY DENSITY FUNCTION; RESONANCE; SPECTROSCOPIC ANALYSIS;

EID: 2242423616     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja027049k     Document Type: Article
Times cited : (49)

References (115)
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    • note
    • PrTACN, 1,4,7-triisopropyl-1,4,7-triazacy-clononane.
  • 61
    • 2242454502 scopus 로고    scopus 로고
    • note
    • Nearly identical results were obtained using the ADF and ORCA software packages, thus justifying our approach to list MO energies and compositions obtained from ADF calculations and to show isosurface plots (Figures 6 and 7) generated from ORCA output.
  • 62
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    • Neese, F. Max Planck Institute for Radiation Chemistry, D-45470 Mülheim/Ruhr, Germany; neese@mpi-muelheim.mpg.de
    • Neese, F. Max Planck Institute for Radiation Chemistry, D-45470 Mülheim/Ruhr, Germany; neese@mpi-muelheim.mpg.de.
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    • note
    • The Ahlrichs (2d, 2p, 2d2fg, and 3p2df) polarization functions were obtained from the TurboMole basis set library under ftp.chemie.uni-karlsruhe.de/pub/basen.
  • 66
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    • The Ahlrichs auxiliary basis sets were obtained from the TurboMole basis set library under ftp.chemie.uni-karlsruhe.de/pub/jbasen: (a) Eichkom, K.; Treutler, O.; Ohm, H.; Haser, M.; Ahlrichs, R. Chem. Phys. Lett. 1995, 240, 283. (b) Eichkorn, K.; Weigend, F.; Treutler, O.; Ahlrichs, R. Theor. Chem. Acc. 1997, 97, 119.
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    • The Ahlrichs auxiliary basis sets were obtained from the TurboMole basis set library under ftp.chemie.uni-karlsruhe.de/pub/jbasen: (a) Eichkom, K.; Treutler, O.; Ohm, H.; Haser, M.; Ahlrichs, R. Chem. Phys. Lett. 1995, 240, 283. (b) Eichkorn, K.; Weigend, F.; Treutler, O.; Ahlrichs, R. Theor. Chem. Acc. 1997, 97, 119.
    • (1997) Theor. Chem. Acc. , vol.97 , pp. 119
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    • note
    • 4 as an external standard, in the present work the 784 cm-1 peak of toluene has been used as an internal standard, giving more accurate results.
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    • See ref 26 and references therein
    • See ref 26 and references therein.
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    • 2242423974 scopus 로고    scopus 로고
    • note
    • 3+.
  • 80
    • 2242457144 scopus 로고    scopus 로고
    • note
    • 3+ centers.
  • 81
    • 2242425760 scopus 로고    scopus 로고
    • note
    • The structure obtained for the corresponding BS state is nearly identical; key interatomic distances read: Ni-0, 1.82/1.85 Å; Ni-S. 2.33 Å, 2.77 Å; and O⋯O, 2.41 Å.
  • 82
    • 2242428404 scopus 로고    scopus 로고
    • note
    • The rms out-of-plane deviation is 0.003 Å.
  • 83
    • 2242450091 scopus 로고    scopus 로고
    • note
    • Ni-O. 1.82/1.83 Å, Ni-S 2.35 Å, Ni⋯Ni, 2.77 Å; and O⋯O, 2.38 Å.
  • 85
    • 2242480557 scopus 로고    scopus 로고
    • note
    • s = 0) dimer spin ground states. As the differences were insignificant, we report here the results of the single-point calculation on the HS geometry, as this calculation yields exact mirror images of the MOs localized on the two halves of the molecule.
  • 86
    • 2242450940 scopus 로고    scopus 로고
    • note
    • xy).
  • 87
    • 2242450092 scopus 로고    scopus 로고
    • note
    • As for the local coordinate system chosen the Ni xz and yz orbitals are strongly mixed in 1, the designations Ni1(xz), α; Ni1(xz), β; Ni1(yz), α; Ni1- (yz), β; Ni2(xz), α; Ni2(xz), β; Ni2(yz), α; and Ni2(yz), β are used solely for labeling purposes.
  • 89
    • 2242449238 scopus 로고    scopus 로고
    • note
    • Note that the HS state is not actually populated at 200 K.
  • 92
    • 2242448370 scopus 로고    scopus 로고
    • note
    • y, orbitals are involved in σ bonding interactions with Ni d orbitals and are therefore strongly stabilized such that corre- sponding excitations lie outside the experimentally accessible range.
  • 93
    • 2242493042 scopus 로고    scopus 로고
    • note
    • g, spin-up MOs are occupied,. their spin-down counterparts are empty in the HS state and therefore can serve as acceptor MOs. The orbital compositions of the spin-up and spin-down MOs are very similar.
  • 94
    • 2242434819 scopus 로고    scopus 로고
    • note
    • The bandwidth of band E in absorption is twice as large as that of band C, suggesting that band E is actually composed of multiple components.
  • 100
    • 2242428403 scopus 로고    scopus 로고
    • note
    • 2 and 0.05 mdyn/Å, respectively, the same values used for 1.
  • 101
    • 2242489505 scopus 로고    scopus 로고
    • note
    • In the model the methyl groups at the pyrazolyl rings were replaced by hydrogen atoms.
  • 102
    • 2242420388 scopus 로고    scopus 로고
    • note
    • 2 orbitals in 4, reflecting the differences in coordination geometry at the Ni sites in 1 and 4.
  • 103
    • 2242459891 scopus 로고    scopus 로고
    • note
    • The energetic ordering of the ligand-derived O (oxo) and S (thioether) ligand orbitals in 1 is based on the experimental observation that the O (oxo) → Ni CT transition is considerably lower in energy than the S (thioether) → Ni CT transitions (Figure 4).
  • 104
    • 2242433903 scopus 로고    scopus 로고
    • note
    • The b and asterisk symbols indicate the bonding and antibonding character of the corresponding bonds.
  • 106
    • 2242459892 scopus 로고    scopus 로고
    • note
    • 2+), dimers: Cu-0 = 1.92 Ä, O-O = 1.41 Å, and Cu⋯Cu = 3.56 Å. See ref 25.
  • 107
    • 2242468814 scopus 로고    scopus 로고
    • note
    • 2-derived MOs in side-on peroxo dimers.
  • 108
    • 2242427487 scopus 로고    scopus 로고
    • note
    • 2 dimers with similar ligands is most probably fortuitous.
  • 111
    • 2242465223 scopus 로고    scopus 로고
    • note
    • tBu) ligands were substituted by methyl groups.
  • 112
    • 2242470665 scopus 로고    scopus 로고
    • note
    • As the difference in total energies of the side-on peroxo and bis-μ -oxo isomers is much larger than the exchange splitting, possible complications associated with determining the relative weights of the spin singlet and triplet contributions to the BS state can be ignored.
  • 113
    • 2242424880 scopus 로고    scopus 로고
    • note
    • The calculated stabilization energy is probably slightly larger than the experimental value because of the truncation of the tert-butyl groups of 1 I and 2 in our computational models; tridentate supporting ligands with sterically demanding substituents are expected to disfavor close metal-metal distances and thus to favor the side-on peroxo structure. See ref 1.
  • 115
    • 2242491289 scopus 로고    scopus 로고
    • note
    • u.


* 이 정보는 Elsevier사의 SCOPUS DB에서 KISTI가 분석하여 추출한 것입니다.