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Volumn 48, Issue 1, 2009, Pages 28-35

Identification of the reactive cis,mer isomer of [lr(CO)2l 3Me]-: Relation to the mechanism of iridium-catalyzed methanol carbonylation

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Indexed keywords


EID: 61849155759     PISSN: 00201669     EISSN: None     Source Type: Journal    
DOI: 10.1021/ic8017858     Document Type: Article
Times cited : (16)

References (38)
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    • This v(CO) band is close to a transient IR absorption at 2032 cm -1 observed after the flash photolysis of la by Volpe et al, ref 6
    • -1 observed after the flash photolysis of la by Volpe et al. (ref 6).
  • 12
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    • In the structure obtained in this study, 3b]AsPh4 crystallizes in a different spacej;roup (P21/c) than that in the structure reported by Volpe et al, P1, ref 6
    • 1/c) than that in the structure reported by Volpe et al. (P1, ref 6).
  • 13
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    • The observed v(CO) frequencies for isotopomers of 1b were modeled by a CO factored force field (based on the analysis by Braterman in Metal Carbonyl Spectra; Academic Press: London, 1975) to give the following C-O stretching (k) and interaction (i) force constants for 1b: kc, 1707.1 N m-1 (CO cis to Me, kt, 1746.7 N m-1 (CO trans to Me, and i, 38.6 N m-1 (see the Supporting Information for calculated v(CO) frequencies, A similar analysis for the cis,fac isomer 1a gives values of kc, 1734 N m-1 and i, 43.2 N m-1. The shift to low frequency of the v(CO) bands of 1b relative to 1a is therefore due to a lower average value of k for the inequivalent CO ligands in 1b despite the higher value of kt
    • t).
  • 14
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    • CH 5.2 Hz, strong doublet with intervening weak singlet.
    • CH 5.2 Hz, strong doublet with intervening weak singlet.
  • 15
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    • 2-. This would result from the reaction of 2d with 1 equiv of CO before complete cleavage of the dimer to give 1b.
    • 2-. This would result from the reaction of 2d with 1 equiv of CO before complete cleavage of the dimer to give 1b.
  • 16
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    • -1):
    • -1):
  • 24
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    • -1 (CCSD(T)).
    • -1 (CCSD(T)).
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    • We note that Ziegler and co-workers calculated that the activation barrier for methyl migration in [Ir(CO)3I2Me] is lower for isomers that have CO trans to methyl ref 22
    • 2Me] is lower for isomers that have CO trans to methyl (ref 22).
  • 26
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    • -1 w.r.t. 4) in which the acetyl ligand displays an agostic C-H-Ir interaction with the vacant cis coordination site.
    • -1 w.r.t. 4) in which the acetyl ligand displays an agostic C-H-Ir interaction with the vacant cis coordination site.
  • 27
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    • - selectively.
    • - selectively.
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    • -1, suggesting that CO loss might be competitive with methyl migration in 1a. These values do not include entropic effects, which are likely significant for a dissociative process.
    • -1, suggesting that CO loss might be competitive with methyl migration in 1a. These values do not include entropic effects, which are likely significant for a dissociative process.
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* 이 정보는 Elsevier사의 SCOPUS DB에서 KISTI가 분석하여 추출한 것입니다.