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Volumn 17, Issue 16, 1998, Pages 3574-3587

Stereochemical investigations of the mechanism of C-H bond activation. Diastereomeric and isotopic scrambling in (Hydrido)alkyliridium complexes

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Indexed keywords


EID: 0001094610     PISSN: 02767333     EISSN: None     Source Type: Journal    
DOI: 10.1021/om980355f     Document Type: Article
Times cited : (21)

References (62)
  • 48
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    • note
    • To determine whether this represents incomplete reaction or the thermodynamic ratio of 2/3 at this temperature, we heated 2a,b at 140°C in dimethylcyclopropane. Unfortunately, we were not able to detect the expected small amount of 3 by NMR spectrometry before irreversible decomposition began to set in. We therefore cannot rigorously establish that the 98/2 ratio of 2/3 represents the equilibrium ratio at this temperature.
  • 50
    • 85034294412 scopus 로고    scopus 로고
    • note
    • 6.
  • 51
    • 85034304254 scopus 로고    scopus 로고
    • note
    • Three Fortran programs were used to fit the data using numerical integration and least-squares nonlinear regression: Gear (v. 2.1) and Git (v. 2.1) were written by R. J. McKinney and F. J. Weigert at E. I. DuPont & Nemours Co., and Calkinetics (v. 1.0) was written by J. Krom (currently at Cornell University). The results obtained using Gear and Git agreed with those using Calkinetics.
  • 52
    • 85034300042 scopus 로고    scopus 로고
    • note
    • In the alkane complex, the iridium center now acts as a prochiral center. To facilitate the discussion: (a) we assume the three atoms, P, Ir, and H (of the alkane ligand), are coplanar with the centroid of the cyclpentadienyl ring; (b) we have arbitrarily defined the direction of insertion of the iridium center into the C-H bond to always proceed toward the second, unbound C-H bond of the alkane ligand; (c) when defining the priority of the C center for stereochemical (R,S) assignments, the H bound to the iridium has the highest priority; this prevents changing of R and S designation solely due to changes in priority. Note that this is not the accepted system for priority.
  • 54
    • 85034278705 scopus 로고    scopus 로고
    • note
    • 60
  • 62
    • 0038560363 scopus 로고
    • Skell, P. S.; Garner, A. Y. J. Am. Chem. Soc. 1956, 78, 5430. J. Org. Chem. 1986, 51, 2386.
    • (1986) J. Org. Chem. , vol.51 , pp. 2386


* 이 정보는 Elsevier사의 SCOPUS DB에서 KISTI가 분석하여 추출한 것입니다.