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Volumn 24, Issue 24, 2005, Pages 6019-6028

A theoretical study of the essential role of DMSO as a solvent/ligand in the Pd(OAc)2/DMSO catalyst system for aerobic oxidation

Author keywords

[No Author keywords available]

Indexed keywords

ACTIVATION ENERGY; CATALYSTS; COMPUTATIONAL METHODS; MOLECULAR STRUCTURE; OXIDATION; REACTION KINETICS;

EID: 28944446576     PISSN: 02767333     EISSN: None     Source Type: Journal    
DOI: 10.1021/om0506217     Document Type: Article
Times cited : (59)

References (42)
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    • (c) Muzart, J. Tetrahedron 2003, 59, 5789-5816.
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    • Muzart, J.1
  • 6
    • 0037028556 scopus 로고    scopus 로고
    • For other mechanistic investigations on Pd-catalyzed aerobic alcohol oxidations, see: (a) Steinhoff, B. A.; Fix, S. R.; Stahl, S. S. J. Am. Chem. Soc. 2002, 124, 766-767.
    • (2002) J. Am. Chem. Soc. , vol.124 , pp. 766-767
    • Steinhoff, B.A.1    Fix, S.R.2    Stahl, S.S.3
  • 19
    • 0034678238 scopus 로고    scopus 로고
    • and references therein
    • The ambidentate character of DMSO is quite remarkable. It has been demonstrated that the mode of DMSO coordination depends strongly on the interaction with the environment and by the effective electonegativity of the ligands coordinated to the metal center. See: Cotton, F. A.; Dikarev, E, V.; Petrukhina, M. A.; Striba, S.-E. Inorg. Chem. 2000, 39, 1748-1754, and references therein.
    • (2000) Inorg. Chem. , vol.39 , pp. 1748-1754
    • Cotton, F.A.1    Dikarev, E.V.2    Petrukhina, M.A.3    Striba, S.-E.4
  • 20
    • 0001608055 scopus 로고
    • 2 both DMSO ligands are S-bond and the complex is dimeric with only one DMSO ligand at each end. See: (a) Bancroft, D. P.; Cotton, F. A.; Verbruggen, M. Acta Crystallogr. Sect. C 1989, 45, 1289-1292. However, the palladium(II) trifluoroacetate crystal structure has one S-bound and one O-bound DMSO.
    • (1989) Acta Crystallogr. Sect. C , vol.45 , pp. 1289-1292
    • Bancroft, D.P.1    Cotton, F.A.2    Verbruggen, M.3
  • 22
    • 22944483170 scopus 로고    scopus 로고
    • (c) Tanaka, D.; Romeril, S. P.; Myers. A, G. J. Am. Chem. Soc. 2005, 127, 10323-10333. Interestingly, X-ray crystallographic characterization of arylpalladium(II) trifluroacetates shows two S-bound DMSO ligands. See ref 5c. Palladium(II) trifluoroacetate structure was computationally evaluated and found in very good agreement with the X-ray crystal structure reported in ref 5c.
    • (2005) J. Am. Chem. Soc. , vol.127 , pp. 10323-10333
    • Tanaka, D.1    Romeril, S.P.2    Myers, A.G.3
  • 23
    • 28944433251 scopus 로고    scopus 로고
    • note
    • 2 is easy to verify directly within one geometry optimization sequence (see details in Supporting Information).
  • 24
    • 28944435158 scopus 로고    scopus 로고
    • PhenS = bathophenanthroline disulfonate, see ref 3e
    • PhenS = bathophenanthroline disulfonate, see ref 3e.
  • 25
    • 28944444125 scopus 로고    scopus 로고
    • note
    • IiPr = 1,3-bis(2,6-diisopropylphenyl)-2,3-dihydro-1H-imidazole; see ref 3h. Oxidation goes with added acid.
  • 26
    • 28944455181 scopus 로고    scopus 로고
    • Private communication
    • Stahl, S. Private communication.
    • Stahl, S.1
  • 28
    • 11444250482 scopus 로고    scopus 로고
    • (b) Stahl et al. has shown that in the case of palladium(0) complexes with nitrogen-based ligands spin crossover dynamics do not influence the overall oxygenation kinetics; see: Landis, C. R.; Morales, C. M.; Stahl, S. S. J. Am. Chem. Soc. 2004, 126, 16302-16303.
    • (2004) J. Am. Chem. Soc. , vol.126 , pp. 16302-16303
    • Landis, C.R.1    Morales, C.M.2    Stahl, S.S.3
  • 29
    • 28944431576 scopus 로고    scopus 로고
    • note
    • 2 (2.15 Å).
  • 30
    • 28944455419 scopus 로고    scopus 로고
    • note
    • Geometry optimization of the Pd(0) with up to eight DMSO ligands was carried out in the gas phase and solvent (PCM). The first coordination sphere of Pd(0) could hold only four sulfur-bonded DMSO; additional ligands were weakly coordinated in the second coordination sphere.
  • 31
    • 28944449505 scopus 로고    scopus 로고
    • note
    • 10 electron configuration of Pd(0) every d orbital is doubly occupied. Symmetric electron distribution means that there are no ligand field effects and the ligand positions are sterically determined.
  • 32
    • 28944432707 scopus 로고    scopus 로고
    • note
    • This effect is well known in physical organic chemistry and is called hyperconjugation.
  • 33
    • 28944452882 scopus 로고    scopus 로고
    • note
    • Hydrogen bonding is characterized by the elongation of the X-H bond, a decrease of its stretch frequency, and an increase of intensity of the respective spectral band. An increase of ED in the σ* orbital is accompanied by weakening of the corresponding bond and its elongation and a concomitant lowering of the X-H stretch frequency.
  • 40
    • 0003934843 scopus 로고
    • Schrödinger, Inc.: Portland, OR
    • Jaguar 4.0; Schrödinger, Inc.: Portland, OR, 1991-2000.
    • (1991) Jaguar 4.0
  • 42
    • 28944454211 scopus 로고    scopus 로고
    • note
    • The use of the effective potential LanL2DZ basis set for thermochemical analysis, namely, for acquiring thermodynamic functions and Gibbs free energy, has regularly been found to result in a level of accuracy comparable to that of superior basis sets to a small fraction of computational costs.


* 이 정보는 Elsevier사의 SCOPUS DB에서 KISTI가 분석하여 추출한 것입니다.