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Volumn 125, Issue 21, 2003, Pages 6394-6408

Spectroscopy and bonding in side-on and end-on Cu2(S2) cores: Comparison to peroxide analogues

Author keywords

[No Author keywords available]

Indexed keywords

ABSORPTION; CHARGE TRANSFER; CHEMICAL BONDS; GROUND STATE; MOLECULAR STRUCTURE; MOLECULAR VIBRATIONS; RESONANCE; SPECTROSCOPIC ANALYSIS;

EID: 0037500145     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja0214678     Document Type: Article
Times cited : (45)

References (77)
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    • II disulfide complexes available in the literature. Other transition metal disulfide complexes have been studied more extensively. For recent reviews, see: Müller, A.; Jaegermann, W.; Enemark, J. H. Coord. Chem. Rev. 1982, 46, 245. Müller, A.; Diemann, E. Adv. Inorg. Chem. 1987, 31, 89. Matsumoto, K.; Sugiyama, H. Acc. Chem. Res. 2002, 35, 915. Wachter, J. Angew. Chem., Int. Ed. 1989, 28, 1613.
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    • Müller, A.1    Jaegermann, W.2    Enemark, J.H.3
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    • II disulfide complexes available in the literature. Other transition metal disulfide complexes have been studied more extensively. For recent reviews, see: Müller, A.; Jaegermann, W.; Enemark, J. H. Coord. Chem. Rev. 1982, 46, 245. Müller, A.; Diemann, E. Adv. Inorg. Chem. 1987, 31, 89. Matsumoto, K.; Sugiyama, H. Acc. Chem. Res. 2002, 35, 915. Wachter, J. Angew. Chem., Int. Ed. 1989, 28, 1613.
    • (1987) Adv. Inorg. Chem. , vol.31 , pp. 89
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    • 0036852611 scopus 로고    scopus 로고
    • II disulfide complexes available in the literature. Other transition metal disulfide complexes have been studied more extensively. For recent reviews, see: Müller, A.; Jaegermann, W.; Enemark, J. H. Coord. Chem. Rev. 1982, 46, 245. Müller, A.; Diemann, E. Adv. Inorg. Chem. 1987, 31, 89. Matsumoto, K.; Sugiyama, H. Acc. Chem. Res. 2002, 35, 915. Wachter, J. Angew. Chem., Int. Ed. 1989, 28, 1613.
    • (2002) Acc. Chem. Res. , vol.35 , pp. 915
    • Matsumoto, K.1    Sugiyama, H.2
  • 22
    • 0024845761 scopus 로고
    • II disulfide complexes available in the literature. Other transition metal disulfide complexes have been studied more extensively. For recent reviews, see: Müller, A.; Jaegermann, W.; Enemark, J. H. Coord. Chem. Rev. 1982, 46, 245. Müller, A.; Diemann, E. Adv. Inorg. Chem. 1987, 31, 89. Matsumoto, K.; Sugiyama, H. Acc. Chem. Res. 2002, 35, 915. Wachter, J. Angew. Chem., Int. Ed. 1989, 28, 1613.
    • (1989) Angew. Chem., Int. Ed. , vol.28 , pp. 1613
    • Wachter, J.1
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    • note
    • 2) complex. See ref 15. Note the electronic transitions are sharpened in the low-temperature absorption spectrum and thus have larger epsilon values.
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    • note
    • 2) complex. See ref 15.
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    • note
    • 2) complex. See ref 15.
  • 47
    • 12444291380 scopus 로고    scopus 로고
    • note
    • 3u mode has very little effect on the calculated S-S force constant and the normal mode descriptions. The fitted Cu-S force constant decreases from 2.33 to 2.02 mdyn/Å (Table S2).
  • 48
    • 12444276902 scopus 로고    scopus 로고
    • note
    • 2) complexes are similar to those reported in the literature using Urey-Bradley force fields. See refs 15 and 17.
  • 49
    • 12444286023 scopus 로고    scopus 로고
    • note
    • 2) complex were not obtained due to photodecomposition of the complex under near-UV illumination.
  • 50
    • 12444285015 scopus 로고    scopus 로고
    • note
    • 2) complex was used in the simulation to account for the temperature effect because the rR excitation profiles were obtained at liquid nitrogen temperature (Figure S2C).
  • 51
    • 12444289755 scopus 로고    scopus 로고
    • note
    • A normal-mode analysis was also performed on the oxyHc vibrational data to get the normal mode eigenvectors. The results are summarized in Table S5. Complete force fields for oxyHc are given in Table S6.
  • 52
    • 12444334868 scopus 로고    scopus 로고
    • note
    • 2) plane.
  • 54
    • 12444260944 scopus 로고    scopus 로고
    • note
    • Unoccupied antibonding MOs are used to describe the bonding since the corresponding occupied bonding orbitals are more mixed due to spin polarization leading to energy proximity with other occupied orbitals. The unoccupied MOs reflect the net contributions to bonding not compensated by electron occupation of antibonding orbitals.
  • 56
    • 12444281189 scopus 로고    scopus 로고
    • note
    • The hydrotris(pyrazolyl)borate ligand positions were kept fixed in the optimization.
  • 57
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    • note
    • 2. Helton, M. E.; Karlin, K. D. Unpublished results.
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    • 12444295697 scopus 로고    scopus 로고
    • note
    • -1.
  • 61
    • 12444340055 scopus 로고    scopus 로고
    • note
    • Cu-S.s vibration mode.
  • 62
    • 12444288786 scopus 로고    scopus 로고
    • note
    • -1 increases the S-S force constant to 2.62 mdyn/A.
  • 63
    • 12444284213 scopus 로고    scopus 로고
    • note
    • S-S intensity ratio obtained from the solid-state rR spectra at corresponding excitation energies.
  • 64
    • 12444316279 scopus 로고    scopus 로고
    • note
    • 2) complex indicates the presence of two electronic transitions under band A (Figure S7).
  • 65
    • 12444342080 scopus 로고    scopus 로고
    • note
    • v CT transitions in the absorption spectrum of the disulfide complex leading to unresolved rR profiles of the symmetric Cu-S vibration.
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    • 2. See: Osafune, K.; Kimura, K. Chem. Phys. Lett. 1974, 25, 47. Wagner, G.; Bock, H. Chem Ber. 1974, 107, 68.
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    • Wagner, G.1    Bock, H.2
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    • note
    • 2) complex.
  • 75
    • 12444300377 scopus 로고    scopus 로고
    • note
    • 2) complex.
  • 76
    • 12444331196 scopus 로고    scopus 로고
    • note
    • Spin-restricted calculations were performed using the ADF2000 package with the VWN local density approximation and Becke-Perdew nonlocal gradient correction, and the ADF basis set IV. Solvation model was used to compensate the high anionic nature of the species, and water was chosen as the solvent. The radii of 1.4 and 1.85 were used for oxygen and sulfur atoms in the solvation model, respectively.


* 이 정보는 Elsevier사의 SCOPUS DB에서 KISTI가 분석하여 추출한 것입니다.